KR101774479B1 - Polymer, organic layer composition, organic layer, and method of forming patterns - Google Patents
Polymer, organic layer composition, organic layer, and method of forming patterns Download PDFInfo
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
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- C08G61/124—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one nitrogen atom in the ring
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- C09D165/00—Coating compositions based on macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Coating compositions based on derivatives of such polymers
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- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
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- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
- C08G2261/324—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed
Abstract
There is provided a polymer comprising a structural unit represented by the following general formula (1), and an organic film composition comprising the same.
[Chemical Formula 1]
The definition of the above formula (1) is as described in the specification.
Description
A novel polymer, an organic film composition comprising the polymer, and a pattern forming method using the organic film composition.
Recently, highly integrated design due to the miniaturization and complexity of electronic devices has accelerated the development of more advanced materials and related processes, so that lithography using existing photoresists also requires new patterning materials and techniques .
In the patterning process, an organic film called a hardmask layer, which is a hard interlayer, can be formed in order to transfer a fine pattern of photoresist to a substrate to a sufficient depth without collapse.
The hard mask layer acts as an interlayer to transfer the fine pattern of the photoresist to the material layer through the selective etching process. Thus, the hardmask layer needs to have corrosion-resisting properties to withstand multiple etching processes.
Meanwhile, it has recently been proposed that the hard mask layer is formed by a spin-on coating method instead of the chemical vapor deposition method. Generally, heat resistance and corrosion resistance are required to be compatible with spin-on characteristics, and an organic film material that can satisfy all of these properties.
One embodiment provides a polymer having good gap-fill and planarization properties while having excellent corrosion resistance and heat resistance.
Another embodiment provides an organic film composition that can simultaneously satisfy both mechanical properties and film flatness.
Another embodiment provides a method of forming a pattern using the organic film composition.
According to one embodiment, there is provided a polymer comprising a structural unit represented by the following formula (1).
[Chemical Formula 1]
In Formula 1,
A 1 and A 2 each independently represents a substituted or unsubstituted aromatic ring group,
B is a divalent organic group,
R 0 to R 8 are each independently selected from the group consisting of hydrogen, a hydroxyl group, a methoxy group, an ethoxy group, a halogen group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C3 to C30 cycloalkenyl group, A substituted or unsubstituted C7 to C20 arylalkyl group, a substituted or unsubstituted C1 to C20 heteroalkyl group, a substituted or unsubstituted C2 to C30 heterocycloalkyl group, a substituted or unsubstituted C2 to C30 hetero A substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C7 to C20 arylalkyl group, a substituted or unsubstituted C1 to C30 alkyl group,
* Is the connection point.
A 1 and A 2 are each independently a divalent group derived from any one selected from the following Group 1, and the divalent group may be a group in which at least one hydrogen atom is substituted or unsubstituted.
[Group 1]
One or two of A 1 and A 2 may be a group in which at least one hydrogen atom is substituted by a hydroxy group.
B in the formula (1) may be represented by the following formula (2).
(2)
In Formula 2,
a and b are each independently an integer of 0 to 2,
L is a divalent group derived from any one selected from the following Group 2, and wherein the divalent group is a divalent group wherein at least one hydrogen atom is substituted or unsubstituted:
[Group 2]
In the group 2,
M is -O-, -S-, -SO 2 - a, or a carbonyl group.
The polymer may have a weight average molecular weight of 500 to 20,000.
According to another embodiment, there is provided an organic film composition comprising a polymer as described above and a solvent.
The polymer may be contained in an amount of 0.1% by weight to 50% by weight based on the total amount of the organic film composition.
According to another embodiment, there is provided an organic film in which the above-mentioned organic film composition is cured to be formed.
The organic layer may include a hard mask layer.
According to another embodiment, there is provided a method of manufacturing a semiconductor device, comprising: providing a material layer on a substrate; applying the organic film composition on the material layer; heat treating the organic film composition to form a hard mask layer; Containing thin film layer; forming a photoresist layer on the silicon-containing thin film layer; exposing and developing the photoresist layer to form a photoresist pattern; Selectively removing the hard mask layer and exposing a portion of the material layer, and etching the exposed portion of the material layer.
The step of applying the organic film composition may be performed by a spin-on coating method.
And forming a bottom anti-reflective layer (BARC) before the step of forming the photoresist layer.
The heat treatment may be performed at a temperature of 100 ° C to 500 ° C.
A novel polymer that has excellent corrosion resistance and heat resistance, and at the same time has good solubility characteristics and can be applied to a spin-on coating system.
Fig. 1 is a reference diagram for explaining the calculation formula 3 for evaluating the planarization characteristic.
Hereinafter, exemplary embodiments of the present invention will be described in detail so that those skilled in the art can easily carry out the present invention. The present invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein.
Unless otherwise defined herein, "substituted" means that the hydrogen atom in the compound is a halogen atom (F, Br, Cl, or I), a hydroxy group, an alkoxy group, a nitro group, a cyano group, an amino group, A thio group, an ester group, a carboxyl group or a salt thereof, a sulfonic acid group or a salt thereof, a phosphoric acid or a salt thereof, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C2 to C20 alkenyl group, a C2 to C20 alkenyl group, A C3 to C30 heteroaryl group, a C3 to C30 heteroaryl group, a C3 to C30 cycloalkyl group, a C3 to C30 aryl group, a C7 to C30 arylalkyl group, a C1 to C30 alkoxy group, a C1 to C20 heteroalkyl group, a C2 to C20 hetero aryl group, Substituted with a substituent selected from a C 1 -C 5 cycloalkenyl group, a C 6 to C 15 cycloalkynyl group, a C 2 to C 30 heterocycloalkyl group, and combinations thereof.
Also, unless otherwise defined herein, "hetero" means containing 1 to 3 heteroatoms selected from N, O, S, Se, Te and P.
Polymers according to one embodiment are described below.
The polymer according to one embodiment comprises a structural unit represented by the following formula (1).
[Chemical Formula 1]
In Formula 1,
A 1 and A 2 each independently represents a substituted or unsubstituted aromatic ring group,
B is a divalent organic group,
R 0 to R 8 are each independently selected from the group consisting of hydrogen, a hydroxyl group, a methoxy group, an ethoxy group, a halogen group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C3 to C30 cycloalkenyl group, A substituted or unsubstituted C7 to C20 arylalkyl group, a substituted or unsubstituted C1 to C20 heteroalkyl group, a substituted or unsubstituted C2 to C30 heterocycloalkyl group, a substituted or unsubstituted C2 to C30 hetero A substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C7 to C20 arylalkyl group, a substituted or unsubstituted C1 to C30 alkyl group,
* Is the connection point.
The polymer includes a structure derived from an indenoindole and a structural unit comprising a divalent organic group which is a linking group.
The polymer comprises an indenoid structure substituted with at least two aromatic ring groups in its structural unit. That is, the substituted or unsubstituted aromatic ring group represented by A 1 and A 2 in the above formula (1) is substituted with an norbornene, so that the polymer can secure a rigid property.
Also, the indenoidal structure includes quaternary carbon.
In the present specification, a quaternary carbon is defined as a carbon in which all four of four hydrogen atoms bonded to carbon are replaced with a group other than hydrogen.
By including the quaternary carbon structure in this way, the polymer minimizes the benzylic hydrogen in the benzylic position and maximizes the ring parameter, thereby securing excellent heat resistance. Further, when a polymer containing a quaternary carbon is used in an organic film composition, the solubility can be improved and it is advantageous to form a film by a spin-on coating method.
In addition, since the indenoidal structure includes nitrogen (N), when the organic film is formed of the polymer, the adhesion to the underlying film, for example, the surface of the silicon wafer is improved and the gap-fill performance and planarization characteristics can be secured have.
R 0 connected to nitrogen (N) in the above formula (1) may be, for example, hydrogen, but is not limited thereto.
For example, in formula (1), A 1 and A 2 each independently represent a substituted or unsubstituted aromatic ring group selected from the following group 1, but the present invention is not limited thereto.
[Group 1]
It is a matter of course that the connection point in the group 1 is not particularly limited.
The aromatic ring groups listed in the group 1 are unsubstituted, but are, for example, a hydroxyl group, a methoxy group, an ethoxy group, a halogen group, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, Or a substituted or unsubstituted C1 to C30 alkoxy group, and the number of substituents may be appropriately selected by those skilled in the art in consideration of the physical properties of the polymer.
For example, in Formula 1, A 1 and / or A 2 may be an aromatic ring group substituted by at least one hydroxy group. In this case, the solubility is improved by the hydrogen bonding of the hydroxy group, The gap-fill performance and the planarization characteristic can be further secured.
B, which represents a linking group in the structural unit represented by the formula (1), may be represented, for example, by the following formula (2).
(2)
In Formula 2,
a and b are each independently an integer of 0 to 2,
L is a divalent group derived from any one selected from the following Group 2, and wherein the divalent group is a divalent group wherein at least one hydrogen atom is substituted or unsubstituted:
[Group 2]
In the group 2,
M is -O-, -S-, -SO 2 - a, or a carbonyl group.
For example, in Formula 2, a and b may each independently be 0 or 1, but are not limited thereto.
The polymer can increase the flexibility of the polymer by including such a linking group in its structural unit. This flexible structure not only improves the solubility by increasing the free volume of the polymer but also improves the gap-fill performance and planarization by increasing the reflow during the baking process by lowering the glass transition temperature (Tg) Can be imported.
The polymer may include a plurality of structural units represented by Formula 1, and the plurality of portions may have the same structure or different structures.
For example, the polymer may have a weight average molecular weight of about 500 to 20,000. By having a weight average molecular weight in the above range, it is possible to optimize by controlling the carbon content of the organic film composition (for example, hard mask composition) containing the polymer and the solubility in solvents.
When the polymer is used as an organic film material, it is possible to form a uniform thin film without forming pin-holes and voids or deteriorate thickness scattering in the baking process, or when a step is present in the lower substrate (or film) It is possible to provide excellent gap-fill and planarization characteristics.
According to another embodiment, there is provided an organic film composition comprising a polymer as described above and a solvent.
The solvent is not particularly limited as long as it has sufficient solubility or dispersibility in the polymer. Examples of the solvent include propylene glycol, propylene glycol diacetate, methoxypropanediol, diethylene glycol, diethylene glycol butyl ether, tri (ethylene glycol) But are not limited to, methyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, cyclohexanone, ethyl lactate, gamma-butyrolactone, N, N-dimethylformamide, , Methyl pyrrolidinone, acetylacetone, and ethyl 3-ethoxypropionate.
The polymer may be included in an amount of about 0.1 to 50% by weight based on the total amount of the organic film composition. By including the polymer in the above range, the thickness, surface roughness, and leveling of the organic film can be controlled.
The organic film composition may further include additives such as a surfactant, a crosslinking agent, a thermal acid generator, and a plasticizer.
The surfactant may be, for example, an alkylbenzenesulfonate, an alkylpyridinium salt, a polyethylene glycol, or a quaternary ammonium salt, but is not limited thereto.
Examples of the cross-linking agent include melamine-based, substitution-based, or polymer-based ones. Preferably, as the crosslinking agent having at least two crosslinking substituents, for example, methoxymethylated glycoluril, butoxymethylated glyceryl, methoxymethylated melamine, butoxymethylated melamine, methoxymethylated benzoguanamine, butoxy Methylated benzoguanamine, a methoxymethylated urea, a butoxymethylated urea, a methoxymethylated thioether, or a methoxymethylated thioether.
As the crosslinking agent, a crosslinking agent having high heat resistance can be used. As the crosslinking agent having a high heat resistance, a compound containing a crosslinking forming substituent group having an aromatic ring (for example, a benzene ring or a naphthalene ring) in the molecule can be used.
The acid generator may be an acidic compound such as p-toluenesulfonic acid, trifluoromethanesulfonic acid, pyridinium p-toluenesulfonic acid, salicylic acid, sulfosalicylic acid, citric acid, benzoic acid, hydroxybenzoic acid or naphthalenecarboxylic acid and / , 4,6-tetrabromocyclohexadienone, benzoin tosylate, 2-nitrobenzyl tosylate, and other organic sulfonic acid alkyl esters, but are not limited thereto.
The additive may be included in an amount of about 0.001 to 40 parts by weight based on 100 parts by weight of the organic film composition. By including it in the above range, the solubility can be improved without changing the optical properties of the organic film composition.
According to another embodiment, there is provided an organic film produced using the organic film composition described above. The organic layer may be in the form of a hardened layer, for example, a hard mask layer, a planarization layer, a sacrificial layer, a filler, etc., and an organic thin film used for electronic devices, .
Hereinafter, a method of forming a pattern using the organic film composition described above will be described.
The method of forming a pattern according to one embodiment includes the steps of providing a material layer on a substrate, applying an organic film composition comprising the polymer and the solvent on the material layer, heat treating the organic film composition to form a hard mask layer Containing thin film layer on the hard mask layer; forming a photoresist layer on the silicon-containing thin film layer; exposing and developing the photoresist layer to form a photoresist pattern; Selectively removing the silicon-containing thin film layer and the hard mask layer using a mask to expose a portion of the material layer, and etching the exposed portion of the material layer.
The substrate may be, for example, a silicon wafer, a glass substrate, or a polymer substrate.
The material layer is a material to be finally patterned and may be a metal layer such as aluminum, copper, or the like, a semiconductor layer such as silicon, or an insulating layer such as silicon oxide, silicon nitride, or the like. The material layer may be formed by, for example, a chemical vapor deposition method.
The organic film composition is as described above, and may be prepared in a solution form and applied by a spin-on coating method. At this time, the coating thickness of the organic film composition is not particularly limited, but may be applied to a thickness of about 50 to 10,000 ANGSTROM.
The heat treatment of the organic film composition may be performed at about 100 to 500 DEG C for about 10 seconds to 1 hour.
The silicon-containing thin film layer may be formed of a material such as SiCN, SiOC, SiON, SiOCN, SiC, SiO and / or SiN.
Further, a bottom anti-reflective coating (BARC) may be further formed on the silicon-containing thin film layer before the step of forming the photoresist layer.
The step of exposing the photoresist layer may be performed using, for example, ArF, KrF or EUV. Further, after the exposure, the heat treatment process may be performed at about 100 to 500 ° C.
The step of etching the exposed portion of the material layer may be performed by dry etching using an etching gas, and the etching gas may be, for example, CHF 3 , CF 4 , Cl 2 , BCl 3 and a mixed gas thereof.
The etched material layer may be formed in a plurality of patterns, and the plurality of patterns may be a metal pattern, a semiconductor pattern, an insulation pattern, or the like, and may be applied to various patterns in a semiconductor integrated circuit device, for example.
Hereinafter, embodiments of the present invention will be described in detail with reference to examples. The following examples are for illustrative purposes only and are not intended to limit the scope of the invention.
Synthetic example
Synthetic example One
(13.2 g, 0.1 mol) and phenylhydrazine (10.8 g, 0.1 mol) were dissolved in acetic acid (319 g), and trifluoroacetic acid . After the addition, the temperature is raised to 120 ° C and reacted for an additional two hours.
After the reaction is terminated, the reaction is cooled slowly to room temperature and the acetic acid is blown off under reduced pressure. 50 mL of a mixed solvent of hexane (Hex) and ethylacetate (EA) (Hex: EA (v: v) = 3: 1) is added to the mixture and stirred to obtain a solid. The resulting solid is washed with 150 mL of the above mixed solvent, and then dissolved in 500 mL of deionized water (DIW), followed by vigorous stirring for 20 minutes. The solid was then filtered again and the residual solvent was removed under reduced pressure to give the following compound 1a.
<Compound 1a>
The obtained compound 1a (15.0 g, 0.07 mol) and potassium hydroxide (20.5 g, 0.35 mol) were dissolved in 150 ml of ethanol, followed by stirring at room temperature for 5 hours.
After the reaction was completed, the solvent was blown off under reduced pressure, and Compound 1b was obtained by column chromatography using a mixed solvent of Hex and EA (Hex: EA (v: v) = 2: 1).
<Compound 1b>
To the flask was added the obtained compound 1b (11.0 g, 0.05 mol), pyrogallol (37.8 g, 0.3 mol), 3-mercaptopropionic acid (2.7 g, 0.03 mol) and DIW (80 g) (68.7 g, 0.7 mol) slowly over 20 minutes. After the addition, the temperature is raised to 80 ° C and the reaction is further carried out for 15 hours.
After the reaction is completed, cool to room temperature and slowly add the reactant to DIW (500 g) under stirring. The resulting solids are filtered and washed three times with DIW (300 g). Then, the solid was added to diethyl ether (300 g), stirred, filtered again, and the residual solvent was removed under reduced pressure to obtain the following compound 1c.
<Compound 1c>
Compound 13c (13.6g, 0.03mol), 1,4-bis (methoxymethyl) benzene (5.0g, 0.03mol) and 68g of propylene glycol monomethyl ether acetate were added to the flask to prepare a solution. Diethylsulfate (0.23 g) was added to the solution, and the mixture was stirred at 100 占 폚 for 10 hours. After the polymerization was completed, the polymer was precipitated in methanol to remove the monomer and low molecular weight to obtain a polymer represented by the following formula (A).
(A)
Synthetic example 2
To the flask was added compound 1b (11.0 g, 0.05 mol), catechol (33.0 g, 0.3 mol), 3-mercaptopropionic acid (2.7 g, 0.03 mol) and DIW (80 g) ) Slowly over 20 minutes. After the addition, the temperature is raised to 80 ° C and the reaction is further carried out for 15 hours.
After the reaction is completed, cool to room temperature and slowly add the reactant to DIW (500 g) under stirring. The resulting solids are filtered and washed three times with DIW (300 g). Then, the solid was added to diethyl ether (300 g), stirred, filtered again, and the residual solvent was removed under reduced pressure to obtain the following compound 2a.
<Compound 2a>
A solution was prepared by adding the obtained compound 2a (12.6 g, 0.03 mol), 1,4-bis (methoxymethyl) benzene (5.0 g, 0.03 mol) and propylene glycol monomethyl ether acetate 68 g. Diethylsulfate (0.23 g) was added to the solution, and the mixture was stirred at 100 占 폚 for 10 hours. Upon completion of the polymerization, the polymer was precipitated in methanol to remove the monomer and low molecular weight to obtain a polymer represented by the following formula (B).
[Chemical Formula B]
Synthetic example 3
2-naphthol (15.9 g, 0.11 mol), 3-mercaptopropionic acid (2.7 g, 0.03 mol) and dioxane (80 g) were placed in a flask and stirred at room temperature. , 0.7 mol) is slowly added over 20 minutes. After the addition, the temperature is raised to 80 ° C and the reaction is further carried out for 15 hours.
After the reaction is completed, cool to room temperature and slowly add the reactant to DIW (500 g) under stirring. The resulting solids are filtered and washed three times with DIW (300 g). Then, the solid was added to diethyl ether (500 g), stirred, filtered again, and the residual solvent was removed under reduced pressure to obtain the following compound 3a.
<Compound 3a>
A solution was prepared by adding the obtained compound 3a (14.7 g, 0.03 mol), 1,4-bis (methoxymethyl) benzene (5.0 g, 0.03 mol) and propylene glycol monomethyl ether acetate 100 g. Diethylsulfate (0.23 g) was added to the solution and the mixture was stirred at 100 占 폚 for 20 hours. When the polymerization was completed, the polymer was precipitated in methanol to remove the monomer and low molecular weight to obtain a polymer represented by the following formula (C).
≪ RTI ID = 0.0 &
Synthetic example 4
To the flask was added compound 1b (11.0 g, 0.05 mol), 1,2-dihydroxynaphthalene (17.6 g, 0.11 mol), 3-mercaptopropionic acid (2.7 g, 0.03 mol) and dioxane (80 g) g, 0.7 mol) is slowly added over 20 minutes. After the addition, the temperature is raised to 80 ° C and the reaction is further carried out for 15 hours.
After the reaction is completed, cool to room temperature and slowly add the reactant to DIW (500 g) under stirring. The resulting solids are filtered and washed three times with DIW (300 g). The solid was then added to diethyl ether (500 g), stirred, filtered again, and the residual solvent was removed under reduced pressure to obtain the following compound 4a.
<Compound 4a>
A solution was prepared by adding the obtained compound 4a (15.6 g, 0.03 mol), 1,4-bis (methoxymethyl) benzene (5.0 g, 0.03 mol) and propylene glycol monomethyl ether acetate 100 g. Diethylsulfate (0.23 g) was added to the solution, and the mixture was stirred at 100 占 폚 for 10 hours. When the polymerization was completed, the polymer was precipitated in methanol to remove the monomer and low molecular weight to obtain a polymer represented by the following formula (D).
[Chemical Formula D]
Comparative Synthetic Example One
After the addition of 28.83 g (0.2 mol) of 1-naphthol, 41.4 g (0.15 mol) of benzoperrylene and 12.0 g (0.34 mol) of paraformaldehyde, 162 g of propylene glycol monomethyl ether acetate (PGMEA) was added to the flask. Next, 0.19 g of p -toluenesulfonic acid monohydrate was added, followed by stirring at 90 to 100 캜 for 5 to 12 hours.
Samples were taken from the polymerization reactants at intervals of 1 hour, and the weight average molecular weight of the sample was measured. When the weight average molecular weight was 1,800 to 2,500, the reaction was completed.
polymerization After completion of the reaction, the reaction product was slowly cooled to room temperature, and the reaction product was added to 40 g of distilled water and 400 g of methanol, stirred vigorously, and allowed to stand. The supernatant was removed, and the precipitate was dissolved in 80 g of propylene glycol monomethyl ether acetate (PGMEA). After stirring vigorously using 320 g of methanol, the solution was allowed to stand (first step). The resulting supernatant was again removed and the precipitate was dissolved in 80 g of propylene glycol monomethyl ether acetate (PGMEA) (second order). The primary and secondary processes were referred to as a one-time purification process, and this purification process was performed three times in total. The purified polymer was dissolved in 80 g of propylene glycol monomethyl ether acetate (PGMEA), and methanol and distilled water remaining in the solution were removed under reduced pressure to obtain an aromatic ring-containing compound represented by the following formula (X).
(X)
Comparative Synthetic Example 2
(0.143 mol) of 9,9'-bis (4-hydroxyphenyl) fluorene, 23.7 g (0.143 mol) of 1,4-bis (methoxymethyl) benzene and 50 g of propylene glycol monomethyl ether acetate To prepare a solution. To the solution was added 1.10 g (7.13 mmol) of diethylsulfate and the mixture was stirred at 100 DEG C for 24 hours. When the polymerization was completed, the polymer was precipitated in methanol to remove the monomer and low molecular weight to obtain a polymer represented by the following formula (Y).
[Formula Y]
Hard mask Preparation of composition
Example One
The polymer obtained in Synthesis Example 1 was dissolved in a solvent of propylene glycol monomethyl ether acetate (PGMEA) and filtered to prepare a hard mask composition. Depending on the intended thickness, the weight of the polymer was adjusted to 3.0 wt% to 15.0 wt% with respect to the total weight of the hard mask composition.
Example 2
A hard mask composition was prepared in the same manner as in Example 1, except that the polymer obtained in Synthesis Example 2 was used in place of the polymer obtained in Synthesis Example 1.
Example 3
A hard mask composition was prepared in the same manner as in Example 1, except that the polymer obtained in Synthesis Example 3 was used in place of the polymer obtained in Synthesis Example 1.
Example 4
A hard mask composition was prepared in the same manner as in Example 1, except that the polymer obtained in Synthesis Example 4 was used in place of the polymer obtained in Synthesis Example 1.
Comparative Example One
Except that propylene glycol monomethyl ether acetate (PGMEA) and cyclohexanone (7: 3 (v / v)) were used instead of the polymer obtained in Synthesis Example 1, A hard mask composition was prepared in the same manner as in Example 1, except that it was dissolved in a mixed solvent.
Comparative Example 2
A hard mask composition was prepared in the same manner as in Example 1, except that the polymer obtained in Comparative Synthesis Example 2 was used in place of the polymer obtained in Synthesis Example 1.
Evaluation 1: Evaluation of heat resistance
The hard mask composition (polymer content: 10.0% by weight) according to Examples 1 to 4 and Comparative Example 1 was spin-coated on a silicon wafer and then heat-treated at 240 ° C for 2 minutes to measure thickness Were measured. Thereafter, the substrate was heat-treated at 400 ° C for 5 minutes to measure the thickness again. From the thickness of the film measured at the two temperatures, the degree of relative heat resistance of the hard mask film was numerically calculated by calculating the thin film thickness reduction ratio based on the following equation (1).
The results are shown in Table 1.
[Equation 1]
Thin film thickness reduction ratio = (Thin film thickness after baking at 400 占 폚 - Thin film thickness after baking at 240 占 폚) / (Thin film thickness after baking at 240 占 폚) X 100 (%)
Decrease (%)
Referring to Table 1, it can be seen that the thin film formed from the hard mask composition according to Examples 1 to 4 has a smaller thickness reduction rate in the heat treatment at 400 degrees Celsius than the thin film formed from the hard mask composition according to the comparative example. From this, it can be seen that the hard mask compositions according to Examples 1 to 4 have higher heat resistance than the hard mask compositions according to the comparative examples.
Evaluation 2: Awareness of corrosion evaluation
The hard mask composition (polymer content: 9.5 wt%) according to Examples 1 to 4 and Comparative Examples 1 and 2 was coated on a silicon wafer by a spin-on coating method on a patterned silicon wafer. Then, a thin film was formed by heat treatment at 400 ° C for 120 seconds, and then the thickness of the thin film was measured using a ST-5000 thin film thickness gauge of K-MAC.
Then, after performing dry etching for 60 seconds each using N 2 / O 2 mixed gas (50mT / 300W / 10O 2 / 50N 2) to the thin film was further measured the thickness of the thin film. The bulk etch rate (BER) was calculated from the thin film thickness before and after the dry etching and the etching time according to the following equation (1).
N 2 / O 2 gas mixture instead of using a CFx gas (100mT / 600W / 42CF 4 / 600Ar / 15O 2) removal rate was calculated by the following equation 2 similarly subjected to dry etching for 120 seconds.
[Equation 2]
Bulk etch rate (BER) = (initial thin film thickness - thin film thickness after etching) / etching time (Å / sec)
The results are shown in Table 2.
Referring to Table 2, the thin films formed from the hard mask compositions according to Examples 1 to 4 had an etching rate for N 2 / O 2 mixed gas and CF x gas as compared to the thin films formed from the hard mask composition according to Comparative Examples 1 and 2 Is low.
From this it can be seen that the hard mask compositions according to Examples 1 to 4 have improved bulk etch properties compared to the hard mask compositions according to Comparative Examples 1 and 2.
Evaluation 3: Evaluation of planarization characteristics
A hard mask composition (polymer content: 5.0% by weight) according to Examples 1 to 4 and Comparative Examples 1 and 2 was spin-on-coated on a patterned silicon wafer and heat treated at 400 ° C for 120 seconds to form a thin film Characteristics were observed.
The planarization characteristics were measured by measuring the thickness of the hard mask layer from the image of the pattern section observed with SEM, and numerically represented by the formula 3 shown in FIG. The planarization characteristics are better as the difference between h1 and h2 is smaller, and the smaller the value, the better the planarization characteristic.
The results are shown in Table 3.
(with or without void)
(1: 2)
(1:10)
Referring to Table 3, the thin film formed from the hard mask composition according to Comparative Examples 1 and 2 has a large difference in h 1 and h 2 , so that not only the planarization degree is poor, but also a void is observed in the pattern, Is also not good.
On the contrary, the thin films formed from the hard mask compositions according to Examples 1 to 4 have a small difference in h 1 and h 2 as compared with the thin films formed from the hard mask composition according to Comparative Examples 1 and 2, Voids were not observed and the gap-fill performance was also good.
While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed exemplary embodiments, And falls within the scope of the invention.
Claims (15)
[Chemical Formula 1]
In Formula 1,
A 1 and A 2 each independently represents a substituted or unsubstituted aromatic ring group,
B is a divalent organic group,
R 0 to R 8 are each independently selected from the group consisting of hydrogen, a hydroxyl group, a methoxy group, an ethoxy group, a halogen group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C3 to C30 cycloalkenyl group, A substituted or unsubstituted C7 to C20 arylalkyl group, a substituted or unsubstituted C1 to C20 heteroalkyl group, a substituted or unsubstituted C2 to C30 heterocycloalkyl group, a substituted or unsubstituted C2 to C30 hetero A substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C7 to C20 arylalkyl group, a substituted or unsubstituted C1 to C30 alkyl group,
* Is the connection point.
Wherein A 1 and A 2 are each independently a divalent group derived from any one selected from the following group 1, and the divalent group is substituted or unsubstituted with at least one hydrogen atom:
[Group 1]
Wherein at least one hydrogen atom of one or both of A 1 and A 2 is substituted by a hydroxy group.
Wherein B is a polymer represented by the following formula:
(2)
In Formula 2,
a and b are each independently an integer of 0 to 2,
L is a divalent group derived from any one selected from the following group 2, and the divalent group is a divalent group substituted or unsubstituted with at least one hydrogen atom:
[Group 2]
In the group 2,
M is -O-, -S-, -SO 2 - a, or a carbonyl group.
A polymer having a weight average molecular weight of 500 to 20,000.
menstruum
: ≪ / RTI >
[Chemical Formula 1]
In Formula 1,
A 1 and A 2 each independently represents a substituted or unsubstituted aromatic ring group,
B is a divalent organic group,
R 0 to R 8 are each independently selected from the group consisting of hydrogen, a hydroxyl group, a methoxy group, an ethoxy group, a halogen group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C3 to C30 cycloalkenyl group, A substituted or unsubstituted C7 to C20 arylalkyl group, a substituted or unsubstituted C1 to C20 heteroalkyl group, a substituted or unsubstituted C2 to C30 heterocycloalkyl group, a substituted or unsubstituted C2 to C30 hetero A substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C7 to C20 arylalkyl group, a substituted or unsubstituted C1 to C30 alkyl group,
* Is the connection point.
Wherein A 1 and A 2 are each independently a bivalent group derived from any one selected from the following group 1, and the bivalent group is substituted or unsubstituted with at least one hydrogen atom:
[Group 1]
Wherein at least one hydrogen atom of one or both of A 1 and A 2 is substituted by a hydroxy group.
And B is an organic film composition expressed by the following formula (2):
(2)
In Formula 2,
a and b are each independently an integer of 0 to 2,
L is a divalent group derived from any one selected from the following group 2, and the divalent group is a divalent group substituted or unsubstituted with at least one hydrogen atom:
[Group 2]
In the group 2,
M is -O-, -S-, -SO 2 - a, or a carbonyl group.
Wherein the polymer has a weight average molecular weight of 500 to 20,000.
Wherein the polymer is contained in an amount of 0.1% by weight to 50% by weight based on the total amount of the organic film composition.
Applying the organic film composition according to any one of claims 6 to 11 on the material layer,
Heat treating the organic film composition to form a hard mask layer,
Forming a silicon-containing thin film layer on the hard mask layer,
Forming a photoresist layer on the silicon-containing thin film layer,
Exposing and developing the photoresist layer to form a photoresist pattern
Selectively removing the silicon-containing thin film layer and the hard mask layer using the photoresist pattern and exposing a portion of the material layer, and
Etching the exposed portion of the material layer
≪ / RTI >
Wherein the step of applying the organic film composition is performed by a spin-on coating method.
Further comprising forming a bottom anti-reflective layer (BARC) before the step of forming the photoresist layer.
Wherein the heat treatment is performed at a temperature of 100 ° C to 500 ° C.
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| JP6670923B2 (en) | 2016-02-24 | 2020-03-25 | 富士フイルム株式会社 | Polycarbonate resin, molded body, optical member and lens |
| KR102116294B1 (en) * | 2017-09-29 | 2020-05-29 | 삼성에스디아이 주식회사 | Polymer, organic layer composition, organic layer, and method of forming patterns |
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| CN108473436B (en) * | 2015-12-28 | 2021-07-06 | 富士胶片株式会社 | Compound, curable composition, cured product, optical component, and lens |
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