KR20180076824A - Method of producimg organic layer, and method of forming patterns - Google Patents

Abstract

Provided is a method for manufacturing an organic film that has excellent planarization characteristics without an extra etchback process or a chemical mechanical polishing (CMP) process. The organic film manufacturing method according to an embodiment of the present invention comprises a first step of applying an organic film composition including an organic compound and a first solvent on a substrate by using a spin-on coating method; and a second step of applying a second solvent having a lower boiling point than the first solvent on the substrate to which an organic film composition is applied by using the spin-on coating method.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method of forming an organic film,

The present invention relates to a method of manufacturing an organic film and a pattern forming method using the organic film, and more particularly, to a method of manufacturing an organic film capable of increasing the degree of planarization of an organic film in forming an organic film on a patterned substrate or a substrate having a step, ≪ / RTI >

BACKGROUND ART [0002] In recent years, the semiconductor industry has developed into an ultrafine technology having a pattern of a few to a few nanometers in a pattern of a size of several hundred nanometers. Effective lithographic techniques are essential to realize this ultrafine technology.

A typical lithographic technique involves forming a material layer on a semiconductor substrate, coating a photoresist layer thereon, exposing and developing the photoresist layer to form a photoresist pattern, and etching the material layer using the photoresist pattern as a mask do.

In recent years, as the size of a pattern to be formed decreases, it is difficult to form a fine pattern having a good profile only by the typical lithographic technique described above. Accordingly, a fine pattern can be formed by forming an organic film called a hardmask layer between the material layer to be etched and the photoresist layer.

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. Therefore, the hard mask layer needs to have heat resistance and resistance to erosion resistance so as to withstand the multiple etching process.

Further, in the case where there is a step on the substrate to be processed, a portion in which the pattern is dense, and a portion where no pattern exists, the film surface needs to be planarized by the hard mask layer. At this time, if the flatness of the hard mask layer is poor, the uniformity of the critical dimension (CD) of the pattern may be lowered in the subsequent pattern formation step, and thus there may be a limit to the implementation of the fine pattern.

One embodiment provides an organic film fabrication method that exhibits excellent planarization characteristics without a separate etchback process or a CMP (Chemical Mechanical Polishing) process.

Another embodiment provides a method of forming a pattern using a film structure according to the above manufacturing method.

According to an embodiment, there is provided a method of manufacturing a thin film transistor, comprising: a first step of applying an organic compound and an organic film composition including a first solvent on a substrate by a spin-on coating method; And a second step of applying a second solvent having a hole transporting property to the organic layer by a spin-on coating method.

The first solvent may have a boiling point of 200 ° C or higher.

The second solvent may have a boiling point of less than 150 < 0 > C.

The first step may include applying the organic film composition on the patterned substrate, and rotating the substrate on which the organic film composition is coated at a speed of 500 rpm to 1,500 rpm.

And further rotating the substrate at a speed of 1,000 rpm to 5,000 rpm after rotating the substrate coated with the organic film composition at a speed of 500 rpm to 1,500 rpm.

Wherein the step of rotating the substrate coated with the organic film composition at a speed of 500 rpm to 1,500 rpm proceeds from 0 second to 10 seconds or less, and further rotating the substrate at a speed of 1,000 rpm to 5,000 rpm comprises 10 seconds To less than 40 seconds.

The second step may include applying the second solvent onto the substrate through the first step, and rotating the substrate on which the second solvent has been applied at a speed of 1,000 rpm to 5,000 rpm.

The rotating process of the second step may proceed for 2 seconds or more and 30 seconds or less.

The first solvent may be selected from the group consisting of benzyl alcohol, diethylene glycol mono ethyl ether, diethylene glycol mono ethyl ether acetate, tetraethylene glycol dimethyl ether, diethylene glycol mono butyl ether, diethylene glycol monobutyl ether acetate (DGBA), triethylene glycol dimethyl ether (TEGDME) But are not limited to, 1-phenoxy-2-propanol, 2-phenoxy ethanol, gamma butyrolactone, tetraethylene glycol, Propylene glycol, tripropylene glycol, triethylene glycol mono butyl ether, dipropylene glycol monobutyl ether, Dipropylene glycol mono butyl ether, benzyl acetate, dioctyl phthalate, dioctyl adipate, terpinyl acetate, 2-hexyloxyethanol ), 2- (2-hexyloxyethoxy) ethanol, tripropylene glycol methyl ether, dipropylene glycol n-butyl ether Dipropylene glycol n-propyl ether, tripropylene glycol n-butyl ether, diethylene glycol monophenyl ether, ethylene glycol monoether, ethylene glycol mono-p-tolyl ether, hexa ethylene glycol, diethylene glycol mono hexyl ether, triethylene glycol diacetate triethylene glycol mono stearate, dipropylene glycol mono propyl ether, dipropylene glycol mono methyl ether acetate, triethylene glycol monoethyl ether, triethylene glycol monooleate, triethylene glycol monooleate, triethylene glycol diacetate, triethylene glycol mono stearate, dipropylene glycol mono propyl ether, Propylene glycol monomethyl ether, triphenyl glycol mono methyl ether, methyl phenyl acetate, oleic alcohol, and the like.

The second solvent may be any one or two selected from the group consisting of ethanol, 2-propanol, toluene, diethyl ether, and ethylene dichloride. Or more.

The flatness of the film measured after the second step may be greater than the flatness of the film measured after the first step.

The method may further include heat treating the thin film after the second step.

The organic compound may contain at least one substituted or unsubstituted benzene moiety in its structure.

According to another embodiment, there is provided a method of manufacturing a semiconductor device comprising the steps of: providing an organic film manufactured according to the above-described method; forming a silicon-containing thin film layer on the organic film; forming a photoresist layer on the silicon- And forming a photoresist pattern by development, and selectively removing the silicon-containing thin film layer and the organic film using the photoresist pattern.

The method may further include forming a bottom anti-reflective layer (BARC) before the step of forming the photoresist.

An organic film excellent in flatness can be produced without a separate planarization process such as etchback or CMP.

FIG. 1 is a flow chart for explaining an organic film manufacturing method according to one embodiment,
2 to 4 are reference views for explaining a pattern forming method according to an embodiment,
5 and 6 are reference views for explaining a method of 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.

In the drawings, the thicknesses are enlarged to clearly indicate layers and regions. Like parts are designated with like reference numerals throughout the specification. Whenever a portion of a layer, film, region, plate, or the like is referred to as being "on" another portion, it includes not only the case where it is "directly on" another portion, but also the case where there is another portion in between. Conversely, when a part is "directly over" another part, it means that there is no other part in the middle.

The singular forms used in this specification include plural forms unless the context clearly dictates otherwise. The word " comprises "and / or" comprising ", as used herein, refers to features, integers, steps, operations, Elements, components, and / or components, but does not preclude the addition of one or more other aspects, numbers, steps, operations, component elements, and / or sets thereof.

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 the group consisting of a cycloalkenyl group, a C 6 to C 15 cycloalkynyl group, a C 2 to C 30 heterocycloalkyl group, and combinations thereof.

Hereinafter, a method of manufacturing an organic film according to one embodiment will be described with reference to FIG.

1 is a flow chart for explaining an organic film manufacturing method according to one embodiment.

Referring to FIG. 1, the organic film manufacturing method includes a first step (S1) of applying an organic film composition on a substrate by a spin-on coating method, and a second step of applying a second solvent on the substrate to which the organic film composition is applied, And a second step (S2) of applying the method of FIG.

First, in the first step (S1), an organic film composition including an organic compound and a first solvent is applied on a substrate by a spin-on coating method.

In a first step Sl, the substrate may be a patterned substrate. The substrate has a plurality of patterns on one surface, and the shape of the pattern is not limited to a triangle, a square, a circle, and the like. The average size (length, width) of the patterns may be, for example, several nanometers to several hundred nanometers, and the average size (length, depth) of the patterns may be several tens of micro Meter.

The substrate may be, for example, a silicon wafer, a glass substrate, or a polymer substrate. Alternatively, the substrate may be a silicon substrate, a silicon nitride, a TiSi, a silicide, a polysilicon tungsten, copper, aluminum, TiN, TaN or a combination thereof on a glass substrate or a polymer substrate.

The organic film composition includes an organic compound as a solid component, and a first solvent.

For example, the organic compound may contain at least one substituted or unsubstituted benzene moiety within its structure. For example, the organic compound may be, for example, a polymer having a weight average molecular weight of 1,000 to 200,000, a monomer having a molecular weight of 500 to 50,000, or a combination thereof. The organic compound may include, for example, 1 wt% to 50 wt%, 5 wt% to 50 wt%, or 5 wt% to 30 wt%, based on 100 wt% of the organic film composition.

The first solvent is not particularly limited as long as it is soluble in the organic compound. For example, the first solvent may be a high boiling point solution having a boiling point of 200 ° C or higher. For example, the boiling point of the first solvent may be selected from the range of 200 ° C to 400 ° C, but is not limited thereto.

For example, the first solvent may include benzyl alcohol, diethylene glycol monoethyl ether, diethylene glycol monoethyl ether acetate, tetraethylene glycol dimethyl But are not limited to, tetraethylene glycol dimethyl ether, diethylene glycol mono butyl ether, diethylene glycol mono butyl ether acetate (DGBA), triethylene glycol dimethyl ether , TEGDME), 1-phenoxy-2-propanol, 2-phenoxy ethanol, gamma butyrolactone, tetraethylene glycol, tripropylene glycol, triethylene glycol mono butyl ether, dipropylene glycol moiety, Dipropylene glycol mono butyl ether, benzyl acetate, dioctyl phthalate, dioctyl adipate, terpinyl acetate, 2-hexyloxyethanol (2- hexyloxyethanol, 2- (2-hexyloxyethoxy) ethanol, tripropylene glycol methyl ether, dipropylene glycol n-butyl ether, dipropylene glycol n-propyl ether, tripropylene glycol n-butyl ether, diethylene glycol monophenyl ether, ethylene glycol Ethylene glycol mono-p-tolyl ether, hexa ethylene glycol, diethylene glycol mono hexyl ether, triethylene glycol But are not limited to, triethylene glycol diacetate, triethylene glycol mono stearate, dipropylene glycol mono propyl ether, dipropylene glycol mono methyl ether acetate, Tripropylene glycol monomethyl ether, methyl phenyl acetate, oleic alcohol, and the like, but is not limited thereto. Examples of the solvent include, but are not limited to, no.

The first step (S1) includes applying the organic film composition onto the substrate, and rotating the substrate coated with the organic film composition at a speed of 500 rpm to 1,500 rpm. The solvent contained in the organic film composition applied on the substrate may be removed while the rotation step is performed. The rotation step of rotating at a speed of 500 rpm to 1,500 rpm can proceed to, for example, more than 0 seconds and less than 10 seconds, and the rotation time can be appropriately selected within the above range in consideration of the concentration of the organic film composition, the solid content, .

Meanwhile, after rotating the substrate coated with the organic film composition at a speed of 500 rpm to 1,500 rpm (a so-called low-speed rotation step), the substrate is then rotated at a speed of 1,000 rpm to 5,000 rpm Rotation phase) can be further roughened. The organic film composition can be uniformly diffused over the substrate (also referred to as a leveling step) through such steps. The rotating step of rotating the substrate at a speed of 1,000 rpm to 5,000 rpm may proceed for 10 seconds or more to 40 seconds or less, and the rotation time may be appropriately adjusted within the above range in consideration of the concentration of the organic film composition, the solid content, You can choose.

The organic film composition may further include additives such as a surfactant, a plasticizer, a crosslinking agent, a thermal acid generator (TAG), and a photoacid generator (PAG). 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.

After the first step (S1) is completed, a second step (S2) of applying a second solvent having a lower boiling point than the first solvent on the substrate to which the organic film composition is applied is applied by a spin-on coating method .

The second solvent is a so-called low boiling solvent having a boiling point lower than that of the above-mentioned first solvent, and may have a boiling point of, for example, less than 150 ° C. The boiling point of the second solvent may be selected within a range of, for example, 70 ° C or more and less than 150 ° C, but is not limited thereto.

The second solvent may have a boiling point range as described above and may be soluble in the first solvent but not substantially soluble in the organic compound. The second solvent may be, for example, ethanol, 2-propanol, or iso-propanol), toluene, diethyl ether, ethylene dichloride ), But the present invention is not limited thereto.

The second step (S2) comprises applying the second solvent onto a substrate through the first step (S1), and applying the substrate on which the second solvent has been applied to substantially the same Spin rate < / RTI > If spin-washing is performed using the second solvent at such a spin rate, the first solvent remaining after the first step (S1) can be effectively removed to form a more flat film.

The rotation speed in the second step may be, for example, 1,000 rpm to 5,000 rpm, and may be, for example, 2 seconds or longer and 30 seconds or shorter, but is not limited thereto. The amount to which the second solvent is applied is not particularly limited and may be appropriately selected in consideration of the size of the substrate, the first solvent, the components of the organic compound, and the like.

The method may further include heat treating the thin film after the second step. The heat treatment step may be performed at, for example, about 100 to 500 DEG C for about 10 seconds to 1 hour.

As described above, the organic film manufacturing method according to one embodiment includes a second step (S2) of applying a predetermined second solvent on a substrate to which an organic film composition is applied after a first step (S1) by a spin-on coating method, The degree of planarization of the organic film produced by removing the first solvent component remaining on the substrate can be increased.

Accordingly, the flatness of the film measured after the second step (S2) shows a level of flatness higher than the flatness of the film measured after the first step (S1). Here, the terms 'flatness', 'flatness degree', 'planarization characteristic', or 'flatness' mean flatness of a thin film, and a film thickness and a pattern of a peri portion where no pattern is formed are formed (I.e., the flatness is large) as long as the difference in the thickness of the cell portion having the smallest difference is not large. There are various methods for measuring the flatness, and one example will be described with reference to FIG. 6, for example. 6 is a cross-sectional view of the substrate to which the organic film composition is applied, h0 is the thickness of the thin film at the portion where the pattern is not formed in the substrate, h1 to h4 are the thicknesses of the thin film on the first to fourth lines Thickness. H0-h1 | + | h0-h2 | + | h0-h3 | + | h0-h4 | + | The smaller the value of + (h0-hn) (n is the number of patterns), the better the flatness.

According to another embodiment, there is provided an organic film produced according to the above-described manufacturing method.

In the film structure, the organic film may be a hard mask layer. Since the hard mask layer has excellent planarization characteristics, it is possible to minimize the CD error of the pattern in the subsequent pattern formation process and improve the CD uniformity of the pattern.

Hereinafter, a pattern forming method according to another embodiment will be described with reference to FIGS. 3 to 5. FIG.

2 to 4 are sectional views for explaining a pattern forming method according to an embodiment.

The pattern forming method includes: providing the organic film; Forming a silicon-containing thin film layer on the organic film; Forming a photoresist layer on the silicon-containing thin film layer; Exposing and developing the photoresist layer to form a photoresist pattern; And selectively removing the silicon-containing thin film layer and the organic film using the photoresist pattern.

Referring to FIG. 2, the organic film 120 described above is formed on the substrate 110. Forming a silicon-containing thin film layer 130 and a photoresist layer 150 sequentially on the organic film 120 and forming a bottom anti-reflective layer (BARC) 140 before forming the photoresist layer 150 As shown in FIG. Further, the method may further include forming a material layer on the substrate before forming the first organic layer (not shown). 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.

For example, the silicon-containing thin film layer 130 may comprise SiCN, SiOC, SiON, SiOCN, SiC, SiN, or combinations thereof.

Referring to FIG. 3, the photoresist layer is exposed and developed to form a photoresist pattern. The step of exposing the photoresist layer may be performed using, for example, ArF, KrF or EUV, but is not limited thereto. Further, after the exposure, the heat treatment process may be performed at about 100 to 500 ° C.

Referring to FIG. 4, the silicon-containing thin film layer 130 and the organic layer 120 in the film structure are selectively removed. A material layer (not shown) may be formed prior to the formation of the organic layer 120 and a portion of the material layer exposed by the step of selectively removing the silicon-containing thin film layer 130 and the organic layer 120 in the film structure may be etched .

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.

Preparation of organic compounds

To the flask was added 4,4'- (9H-fluorene-9,9-diyl) diphenol (35g, 0.1mol), 1,4-bis (methoxymethyl) benzene (17g, 0.1mol), 0.5g diethylsulfate, 82 g of monomethyl ether acetate (PGMEA) was added, and the mixture was stirred at 100 DEG C for 2 to 15 hours to carry out a polymerization reaction. Samples were taken from the polymerization reactants at intervals of 1 hour and the reaction was completed when the weight average molecular weight was 2,000 to 3,500. After completion of the polymerization reaction, the reaction product was slowly cooled to room temperature, and then the reaction product was added to 40 g of distilled water and 400 g of methanol, stirred vigorously, and allowed to stand to form a precipitate. The resulting precipitate was dissolved in 80 g of propylene glycol monomethyl ether acetate (PGMEA), and then 320 g of methanol and 320 g of water were stirred vigorously to form a precipitate. The resulting precipitate was dissolved again in 80 g of propylene glycol monomethyl ether acetate (PGMEA). The above-described purification step of forming the precipitate twice 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 a polymer (weight average molecular weight: 3,700) having a structural unit represented by the following formula (1) ≪ / RTI >

[Chemical Formula 1]

Organic film  Produce

Example  One

The polymer of Formula 1 was dissolved in gamma-butyrolactone to prepare an organic film composition. The content of the polymer relative to 100 wt% of the organic film composition was 10 wt%.

The organic film composition was coated on a patterned silicon wafer at 1,000 rpm for 5 seconds to allow the hard mask composition to diffuse onto the wafer, and then rotated at 1,500 rpm for 20 seconds and accelerated at 3,000 rpm. Subsequently, 5 g of toluene was injected, and the sample was further dried by rotating at 3,000 rp for 10 seconds. Baked at 240 DEG C for 1 minute to adjust the thickness of the thin film formed from the organic film composition measured at the patternless portion on the wafer to 2,000 ANGSTROM. In the examples and comparative examples of the present invention, spin coating was conducted using Mikasa, MS-A200 spin coater.

Example  2

The polymer of Formula 1 was dissolved in dipropylene glycol monomethyl ether acetate to prepare an organic film composition. The content of the polymer relative to 100 wt% of the organic film composition was 10 wt%.

The organic film composition was coated on a patterned silicon wafer at 1,000 rpm for 5 seconds to allow the hard mask composition to diffuse onto the wafer, and then rotated at 1,500 rpm for 20 seconds and accelerated at 3,000 rpm. Subsequently, 5 g of toluene was injected, and the sample was further dried by rotating at 3,000 rp for 10 seconds. Baked at 240 DEG C for 1 minute to adjust the thickness of the thin film formed from the organic film composition measured at the patternless portion on the wafer to 2,000 ANGSTROM.

Example  3

The polymer of Formula 1 was dissolved in dipropylene glycol n-butyl ether to prepare an organic film composition. The content of the polymer relative to 100 wt% of the organic film composition was 10 wt%.

The organic film composition was coated on a patterned silicon wafer at 1,000 rpm for 5 seconds to allow the hard mask composition to diffuse onto the wafer, and then rotated at 1,500 rpm for 20 seconds and accelerated at 3,000 rpm. Subsequently, 5 g of isopropanol (also referred to as iso-propanol or 2-propanol) was injected, and further rotated at 3,000 rpm for 10 seconds to dry the sample. Baked at 240 DEG C for 1 minute to adjust the thickness of the thin film formed from the organic film composition measured at the patternless portion on the wafer to 2,000 ANGSTROM.

Example  4

The polymer of Formula 1 was dissolved in benzyl alcohol to prepare an organic film composition. The content of the polymer relative to 100 wt% of the organic film composition was 10 wt%.

The organic film composition was coated on a patterned silicon wafer at 1,000 rpm for 5 seconds to allow the hard mask composition to diffuse onto the wafer, and then rotated at 1,500 rpm for 20 seconds and accelerated at 3,000 rpm. Subsequently, 5 g of iso-propanol was injected, and further rotated at 3,000 rpm for 10 seconds to dry the sample. Baked at 240 DEG C for 1 minute to adjust the thickness of the thin film formed from the organic film composition measured at the patternless portion on the wafer to 2,000 ANGSTROM.

Comparative Example  One

The polymer of Formula 1 was dissolved in propylene glycol monomethyl ether acetate (PGMEA) to prepare an organic film composition. The content of the polymer relative to 100 wt% of the organic film composition was 10 wt%.

Subsequently, the organic film composition was spin-coated on the patterned silicon wafer at 1,500 rpm and baked at 240 캜 for 1 minute to measure the thickness of the thin film formed from the organic film composition measured on the patternless portion on the wafer to 2,000 Å .

Comparative Example  2

The polymer of Formula 1 was dissolved in gamma-butyrolactone to prepare an organic film composition. The content of the polymer relative to 100 wt% of the organic film composition was 10 wt%.

Subsequently, the organic film composition was spin-coated on the patterned silicon wafer at 1,500 rpm and baked at 240 캜 for 1 minute to measure the thickness of the thin film formed from the organic film composition measured on the patternless portion on the wafer to 2,000 Å .

Comparative Example  3

The polymer of Formula 1 was dissolved in gamma-butyrolactone to prepare an organic film composition. The content of the polymer relative to 100 wt% of the organic film composition was 10 wt%.

Subsequently, the organic film composition was spin-coated on the patterned silicon wafer at 1,500 rpm, immersed in ethanol for 60 seconds, and baked at 240 DEG C for 1 minute to measure the organic The thickness of the thin film formed from the film composition was adjusted to 2,000 ANGSTROM.

Rating 1: Coating property

The organic film compositions used in Examples 1 to 4 and Comparative Examples 1 to 3 were coated on a silicon wafer without a pattern, and it was confirmed whether there was a macroscopic change in the coated film over time in the unbaked state .

The results are shown in Table 1.

Coating property observation Example 1 No change Example 2 No change Example 3 No change Example 4 No change Comparative Example 1 No change Comparative Example 2 Curling of edges Comparative Example 3 Partial peeling occurs

Referring to Table 1, the thin films prepared according to Examples 1 to 4 showed no change in the film after the process, but the thin films produced according to Comparative Examples 1 to 3 showed a continuous film change after the process. Accordingly, it can be seen that the thin films prepared according to Examples 1 to 4 can perform the subsequent processes more stably than the thin films prepared according to Comparative Examples 1 to 3.

Evaluation 2: Gap-fill and planarization characteristics (1)

Gap-fill characteristics and planarization characteristics of the thin films prepared according to Examples 1 to 4 and Comparative Examples 1 to 3 were evaluated.

 The gap-fill characteristics were evaluated by observing the cross-section of the thin film with FE-SEM (Hitachi, S-4800) to determine void formation. The planarization characteristics were measured by measuring the thickness of the thin film from the image of the cross-section of the pattern observed by FE-SEM and calculating the flatness according to the planarization equation shown in FIG.

Referring to FIG. 5, h ₁ denotes a value obtained by averaging thicknesses of thin films measured at arbitrary three points where no pattern is formed on the substrate, h ₂ denotes a value measured at any three points where a pattern is formed on the substrate Means the thickness of one thin film. The aspect ratio of the substrate pattern is 1: 3. Referring to FIG. 5, the planarization characteristic is superior as the difference between h ₁ and h ₂ is small.

The results are shown in Table 2.

Planarization and Gap-Fill Characteristics Planarity (%) Gap-Fill Characteristics Example 1 8.92 No Void Example 2 11.67 No Void Example 3 14.27 No Void Example 4 12.95 No Void Comparative Example 1 51.68 No Void Comparative Example 2 _- Void Occurrence Comparative Example 3 - Void Occurrence

Referring to Table 2, in Comparative Example 1, the difference between h1 and h2 is large and the degree of planarization is not so good. In Comparative Examples 2 to 3, voids are observed in the pattern, have. As described in Evaluation 1, the thin films according to Comparative Examples 2 to 3 were not able to measure the flatness because the coating properties were not secured.

On the other hand, it was confirmed that the thin films according to Examples 1 to 4 had a good gap-fill performance to the extent that voids were not observed, and that the difference in h1 and h2 was small compared to Comparative Example 1, .

Evaluation 3: Planarization characteristics (2)

The planarization characteristics of the thin films prepared according to Examples 1 to 4 and Comparative Example 1 were evaluated.

In FIG. 6, P represents a region where no pattern is formed, that is, a Peri region, and C represents a region where a pattern is formed, that is, a cell region.

Flattening properties were measured for the step to be defined by the _{│h 0 -h 1 │ + │h 0} -h 2 │ + │h 0 -h 3 │ + │h 0 -h 4 │ in FIG. Referring to FIG. 6, h ₀ is the thickness of the thin film at the portion where the pattern is not formed on the substrate, and h ₄ is the thickness of the thin film on the fourth line at the beginning of the pattern. The width of the pattern is 200 nanometers and the L / S ratio is 1/1.

Referring to FIG. 6, the planarization characteristic is expressed by the following equation: H ₀ -h ₁ + | h ₀ -h ₂ | + | h ₀ -h ₃ | + | h ₀ -h ₄ | The better it is.

The results are shown in Table 3.

Step sum (A) Example 1 73 Example 2 116 Example 3 142 Example 4 127 Comparative Example 1 531

Referring to Table 3, it can be seen that the thin films according to Examples 1 to 4 have a small sum of steps as compared with the thin film according to Comparative Example 1, and thus the flatness is excellent.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed exemplary embodiments, And falls within the scope of the invention.

110: substrate 120: organic layer
130: Silicon-containing thin film layer 140: Antireflection layer
150: photoresist layer

Claims (15)

A first step of applying an organic compound and an organic film composition including a first solvent on a substrate by a spin-on coating method, and
A second step of applying a second solvent having a boiling point lower than that of the first solvent on a substrate to which the organic film composition is applied by a spin-on coating method,
Containing
Organic film manufacturing method. The method of claim 1,
Wherein the first solvent has a boiling point of 200 ° C or higher. The method of claim 1,
Wherein the second solvent has a boiling point of less than < RTI ID = 0.0 > 150 C. < / RTI > The method of claim 1,
Wherein the first step comprises applying the organic film composition onto the patterned substrate and rotating the substrate on which the organic film composition has been applied at a speed of 500 rpm to 1,500 rpm
Organic film manufacturing method. 5. The method of claim 4,
After the step of rotating the substrate coated with the organic film composition at a speed of 500 rpm to 1,500 rpm,
Further rotating the substrate at a rate of from 1,000 rpm to 5,000 rpm
Organic film manufacturing method. The method of claim 5,
Wherein the step of rotating the substrate coated with the organic film composition at a speed of 500 rpm to 1,500 rpm proceeds from 0 to less than 10 seconds,
Wherein the step of further rotating the substrate at a speed of 1,000 rpm to 5,000 rpm is performed for 10 seconds to 40 seconds
Organic film manufacturing method. The method of claim 1,
Wherein the second step comprises applying the second solvent onto the substrate through the first step and rotating the substrate on which the second solvent has been applied at a speed of from 1,000 rpm to 5,000 rpm
Organic film manufacturing method. 8. The method of claim 7,
Wherein the step of rotating the organic light emitting layer in the second step progresses from 2 seconds to 30 seconds or less. The method of claim 1,
The first solvent may be selected from the group consisting of benzyl alcohol, diethylene glycol mono ethyl ether, diethylene glycol mono ethyl ether acetate, tetraethylene glycol dimethyl ether, diethylene glycol mono butyl ether, diethylene glycol monobutyl ether acetate (DGBA), triethylene glycol dimethyl ether (TEGDME) But are not limited to, 1-phenoxy-2-propanol, 2-phenoxy ethanol, gamma butyrolactone, tetraethylene glycol, Propylene glycol, tripropylene glycol, triethylene glycol mono butyl ether, dipropylene glycol monobutyl ether, Dipropylene glycol mono butyl ether, benzyl acetate, dioctyl phthalate, dioctyl adipate, terpinyl acetate, 2-hexyloxyethanol ), 2- (2-hexyloxyethoxy) ethanol, tripropylene glycol methyl ether, dipropylene glycol n-butyl ether Dipropylene glycol n-propyl ether, tripropylene glycol n-butyl ether, diethylene glycol monophenyl ether, ethylene glycol monoether, ethylene glycol mono-p-tolyl ether, hexa ethylene glycol, diethylene glycol mono hexyl ether, triethylene glycol diacetate triethylene glycol mono stearate, dipropylene glycol mono propyl ether, dipropylene glycol mono methyl ether acetate, triethylene glycol monoethyl ether, triethylene glycol monooleate, triethylene glycol monooleate, triethylene glycol diacetate, triethylene glycol mono stearate, dipropylene glycol mono propyl ether, Wherein the organic solvent is selected from the group consisting of tripropylene glycol mono methyl ether, methyl phenyl acetate, and oleic alcohol. The method of claim 1,
The second solvent may be any one or two selected from the group consisting of ethanol, 2-propanol, toluene, diethyl ether, and ethylene dichloride. Or more. The method of claim 1,
Wherein the flatness of the film measured after the second step is greater than the flatness of the film measured after the first step. The method of claim 1,
Further comprising the step of heat-treating the thin film after the second step. The method of claim 1,
Wherein the organic compound contains at least one substituted or unsubstituted benzene moiety in its structure. Providing an organic film produced according to any one of claims 1 to 13,
Forming a silicon-containing thin film layer on the organic film,
Forming a photoresist layer on the silicon-containing thin film layer,
Exposing and developing the photoresist layer to form a photoresist pattern, and
Selectively removing the silicon-containing thin film layer and the organic film using the photoresist pattern
≪ / RTI > The method of claim 14,
And forming a bottom anti-reflective layer (BARC) before the step of forming the photoresist.

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