CN112947012A - Photosensitive resin, thinner composition for removing antireflection film, and photosensitive resin and antireflection film removing method using same - Google Patents

Abstract

The present invention provides a diluent composition comprising: a) C2-C4 alkylene glycol C1-C4 alkyl ether acetate; b) cyclopentanone; c) the invention also provides a photosensitive resin and a method for removing the anti-reflection film.

Description

Photosensitive resin, thinner composition for removing antireflection film, and photosensitive resin and antireflection film removing method using same

Technical Field

The present invention relates to a photosensitive resin and a thinner composition for removing an antireflection film, which are used in a process for manufacturing a semiconductor device and a thin film transistor liquid crystal display device, and a method for removing a photosensitive resin and an antireflection film using the same.

Background

In the manufacturing process of a semiconductor device, a photolithography process is one of important processes in which a photosensitive resin composition is applied to a wafer, a previously designed pattern is transferred, and then an electronic circuit is formed by an appropriate etching process according to the transferred pattern.

The photolithography process comprises 1) coating step for uniformly coating photosensitive resin composition on the surface of wafer; 2) a soft baking (soft baking) process of evaporating a solvent from the coated photosensitive film to attach the photosensitive film to the wafer surface; 3) an exposure step of repeatedly and sequentially performing reduction projection on the circuit pattern on the photomask by using a light source such as ultraviolet rays, and exposing the photosensitive film to transfer the pattern of the photomask to the photosensitive film; 4) a developing process of selectively removing portions having different physical properties (e.g., poor solubility) according to the light exposure to the light source using a developing solution; 5) a hard baking step of more tightly fixing the photosensitive film remaining on the wafer after the developing step; 6) an etching step of etching a predetermined portion in accordance with the developed pattern of the photosensitive film; 7) a peeling process of removing the unnecessary photosensitive film after the process; and the like.

In the photolithography technique, a spin coating process of providing a photosensitive film on a wafer and rotating the substrate so that the surface is uniformly scattered due to a centrifugal force, which deposits the photosensitive film on the edge portion and the back surface of the substrate due to the centrifugal force to form small spherical matters. The spherical material is peeled off during the transfer of the substrate after the baking process, thereby forming a cause of particles in the device and a cause of defocusing during exposure. These unnecessary photosensitive substances cause device contamination, thereby lowering productivity in the manufacturing process of the element, and in order to remove these unnecessary photosensitive substances, ejection nozzles are provided above and below the edge portion and the back surface portion of the substrate, through which a thinner composition composed of an organic solvent component is ejected to the edge portion and the back surface portion to perform removal.

Factors that determine the performance of the diluent composition are, for example, dissolution rate and volatility. The dissolution rate of the thinner composition is particularly important as an ability to effectively and rapidly dissolve and remove the photosensitive resin. Specifically, in the cleaning of the edge portion, it is necessary to have a proper dissolution rate to have a smooth processing section, and the erosion (attack) of the photosensitive film occurs when the dissolution rate is too high. On the contrary, a trailing (tail) flow phenomenon of a partially dissolved photosensitive film called trailing (tailing) occurs in cleaning of the photosensitive film applied on the substrate when the dissolution rate is too low. Particularly in recent years, due to the increase in the diameter of a substrate with higher integration and higher density of a semiconductor integrated circuit, a low spin rotation speed is inevitably generated in a cleaning process by a spin coater. In the cleaning process, since the substrate is shaken at a low rotation speed and the contact speed of the sprayed thinner composition does not have an appropriate dissolution speed, a bouncing (bouncing) phenomenon occurs to increase the use of the thinner composition unnecessarily. Compared with the conventional high spin cleaning process, the low spin cleaning process due to the increase in the diameter of the substrate requires a strong dissolution rate of the diluent.

In addition, the volatility needs to be so volatile that no residue remains on the substrate surface after the photosensitive resin is removed. If the volatility is too low and the composition fails to volatilize and remains, the remaining diluent itself acts as a contamination source in various steps, particularly in a subsequent etching step or the like, and the productivity of semiconductor elements is lowered. When the volatility is too high, the substrate is rapidly cooled to cause a phenomenon that the thickness deviation of the coated photosensitive film is severe and is easily volatilized into the air in use to become a cause of contamination of the cleaning property itself. Thus, defects such as various streaks and erosion of the photosensitive film directly cause a reduction in the production yield of the semiconductor device.

Korean laid-open patent No. 10-2005-0080603 discloses a composition comprising propylene glycol monoalkyl ether acetate, ethyl 3-ethoxypropionate, and the like. However, the thinner composition contains methyl 3-methoxypropionate having a high volatility, and thus has problems of uneven thickness and edge cracking. In addition, in order to improve the solubility of a highly polar photoresist and EBR (Edge Bead Removal) characteristics, a conventional thinner composition includes a highly polar composition, and when the polarity is too high, the photoresist swells (swells) at the end of the EBR toward the center of the wafer, thereby increasing the peak height (Hump height). In addition, since a high peak height causes problems such as a decrease in usable area and an increase in defective rate and a decrease in productivity due to humping (Hump) in a subsequent process, there is a strong demand for solving these problems.

Documents of the prior art

Patent document

(patent document 1) KR 10-2005-0080603A

Disclosure of Invention

Technical problem

In order to solve the problems of the prior art, it is an object of the present invention to provide a thinner composition having a property of uniformly removing an unnecessary photosensitive film generated on an edge portion or a back surface portion of a substrate for manufacturing a semiconductor device and a thin film transistor liquid crystal display device due to an increase in diameter of the substrate.

In particular, an object of the present invention is to provide a thinner composition having excellent solubility and EBR characteristics for an anti-reflective film as well as a photosensitive film including a photoresist for KrF, ArF and EUV, and capable of reducing a peak height.

Further, an object of the present invention is to provide a thinner composition having a better effect than the prior art, having no toxicity to a human body, no unpleasant odor, and thus having high operation stability.

Technical scheme

To achieve the object, the present invention provides a diluent composition comprising: a) C2-C4 alkylene glycol C1-C4 alkyl ether acetate; b) cyclopentanone; c) a compound represented by the following chemical formula 1:

[ chemical formula 1 ]

In the chemical formula 1, R₁Is C1-C4 alkyl, R₂Is C2-C4 alkyl.

The present invention includes a method for removing a photosensitive resin, the method comprising: a step of removing the photosensitive resin on the substrate using the thinner composition.

The present invention includes a method for removing an antireflection film, the method including: and a step of removing the antireflection film on the substrate by using the thinner composition.

Advantageous effects

The diluent composition according to the present invention has the following effects: the thinner composition is used for the edge portion and the back portion of a substrate used in a method for manufacturing a semiconductor device and a thin film transistor liquid crystal display device, thereby effectively removing an unnecessary photosensitive film adhered thereto in a short time.

Particularly, a thinner composition is provided which has excellent solubility and EBR characteristics for a resist for KrF, ArF and EUV (extreme ultraviolet) and can reduce the peak height of an antireflection film.

Further, the polarity of the thinner composition is adjusted to reduce the swelling (swelling) rate of the photoresist toward the center of the wafer at the EBR end by the thinner, thereby reducing the peak height (Hump height), thereby increasing the usable area, reducing the defect rate due to Hump (Hump) in the subsequent process, and improving the productivity.

In addition, the thinner composition of the present invention has no toxicity to the human body, no offensive odor to thereby have high operational stability, and low corrosiveness to thereby prevent the erosion of the substrate to be cleaned.

Drawings

Fig. 1 is a graph for calculating peak heights in an EBR (Edge Bead Removal) test of experimental example 1.

Fig. 2a is a photograph taken after the EBR process is performed in the EBR (Edge Bead Removal) test of experimental example 1 (a state in which the EBR line has no uniformity and a tailing phenomenon is generated).

Fig. 2b is a photograph taken after the EBR process is performed in the EBR (Edge Bead Removal) test of experimental example 1 (state where the EBR line does not have linearity and uniformity).

Fig. 2c is a photograph taken after the EBR process is performed in the EBR (Edge Bead Removal) test of experimental example 1 (state where the EBR line has no linearity but has uniformity). Fig. 2d is a photograph taken after the EBR process is performed in the EBR (Edge Bead Removal) test of experimental example 1 (the linearity and uniformity of the EBR line are constant).

Fig. 3a is a photograph taken after the RRC process is performed in the RRC (reduced Resist Coating) test of experimental example 2 (a state where the photosensitive film on the wafer is coated by 80% or less).

FIG. 3b is a photograph taken after the RRC process was performed in the RRC (reduced Resist Coating) test of Experimental example 2 (state where the photosensitive film on the wafer was coated by 80 to 95%).

Fig. 3c is a photograph taken after the RRC procedure was performed in the RRC (reduced Resist Coating) test of experimental example 2 (the photosensitive film on the wafer was coated by 95% or more, but had stains or uncoated portions).

Fig. 3d is a photograph taken after the RRC procedure was performed in the RRC (reduced Resist Coating) test of experimental example 2 (the photosensitive film on the wafer was coated by 95% or more, and was free from stains).

Detailed Description

The present invention provides a diluent composition comprising: a) C2-C4 alkylene glycol C1-C4 alkyl ether acetate; b) cyclopentanone; c) a compound represented by the following chemical formula 1:

[ chemical formula 1 ]

In the chemical formula 1, R₁Is C1-C4 alkyl, R₂Is C2-C4 alkyl.

The thinner composition of the present invention is preferably used for removing a photosensitive resin and/or an antireflection film used in a process for manufacturing a semiconductor device, a thin film transistor, and a liquid crystal display device. The photosensitive resin is at least one of ArF, KrF and EUV photoresist.

The thinner composition according to the present invention has excellent solubility and EBR characteristics for a photosensitive resin and/or an anti-reflective coating including a Photoresist (PR) for KrF, ArF and EUV, and can reduce a peak height. Further, the polarity of the thinner composition is adjusted so that the thinner reduces the swelling (swelling) speed of the Photoresist (PR) toward the center of the wafer at the end of the EBR, thereby improving productivity.

Specifically, when removing unnecessary portions of the photosensitive resin and/or the antireflection film formed on the substrate (wafer), as shown in the upper end of fig. 1, the edge portion of the photosensitive resin and/or the antireflection film swells to form a level difference higher than the photosensitive resin and/or the antireflection film portion other than the edge portion, which is referred to as Hump (Hump), and the level difference is referred to as peak height (Hump height)

In addition, the thinner composition of the present invention further comprises a calculated polarity value of solubility parameter of 7MPa^1/2～8MPa^1/2Thereby improving the solubility of the photoresist to improve the EBR characteristics. The Solubility Parameter in the present invention refers to the Hansen Solubility Parameter (Hansen Solubility Parameter). Specifically, when the calculated value of the polarity including the solubility parameter is 7MPa^1/2～8MPa^1/2Has excellent EBR characteristics and reduces the peak height.

In addition, the thinner composition of the present invention has no toxicity to the human body, no offensive odor to thereby have high operational stability, and low corrosiveness to thereby prevent the erosion of the substrate to be cleaned.

< thinner composition >

The diluent composition of the present invention comprises: a) C2-C4 alkylene glycol C1-C4 alkyl ether acetate; b) cyclopentanone; c) a compound represented by the following chemical formula 1.

a) C2-C4 alkylene glycol C1-C4 alkyl ether acetate

In the present invention, the C2-C4 alkylene glycol C1-C4 alkyl ether acetate has excellent solubility to all kinds of photoresists and imparts uniform coating ability to the photoresists.

The C2-C4 alkylene glycol C1-C4 alkyl ether acetate is preferably at least one selected from the group consisting of propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, and mixtures thereof. In particular, at least one selected from the group consisting of propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and mixtures thereof is more preferable.

The C2-C4 alkylene glycol C1-C4 alkyl ether acetate composition is preferably contained in an amount of 30-80 wt% based on the total weight of the diluent composition of the present invention. When the range is satisfied, the solubility to all photoresists is excellent, and an appropriate surface tension is achieved to uniformly coat the photoresist. When exceeding the range, the surface tension becomes high so that the photoresist is not uniformly spread when coated, and the phenomenon that the edge is cracked due to a minute pattern step on the wafer cannot be overcome.

b) Cyclopentanone

The cyclopentanone contained in the thinner composition of the present invention has a cyclic structure in structure, has a good affinity with cyclic resin, and has a high polarity (calculated polarity of solubility parameter: 7.9 MPa)^1/2) Thereby increasing the polarity of the thinner composition and improving the solubility and dissolution rate of the photoresist or anti-reflective coating having high polarity such as KrF, ArF and EUV; and reduces the phenomenon that gamma-butyrolactone having low volatility among high polarity and, in contrast, PR having high volatility flows at the end in a drying process at the end of the EBR process.

In particular, the cyclopentanone has higher volatility and excellent solubility than cyclohexanone, and the thinner composition of the present invention provides more excellent effects in EBR or RRC than the prior art, has less harmful effects on the human body and no unpleasant odor upon inhalation or contact with the eyes or skin, and thus greatly improves the working stability.

Meanwhile, the cyclopentanone causes a difference in photoresist dissolution rate and volatility in comparison with a linear ketone (e.g., methyl ethyl ketone, methyl amyl ketone, etc.) according to its structure, and thus a disadvantage that linearity of EBR lines to a photosensitive film after EBR cannot be achieved or uniformity cannot be obtained even if linearity is achieved is not applicable to the present invention.

The cyclopentanone is preferably included in an amount of 10 to 50 wt%, more preferably 15 to 40 wt%, based on the entire weight of the composition. When the range is satisfied, excellent dissolution activity is provided for all photoresists, and appropriate surface tension is achieved to provide excellent RRC and EBR characteristics.

Specifically, when cyclopentanone is out of the range, the dissolving power may be reduced to cause EBR failure, and the volatility of the diluent composition may be increased to cause coating thickness non-uniformity.

c) A compound represented by the following chemical formula 1

The thinner composition of the present invention comprises a compound represented by the following chemical formula 1 as a solvent propionate compound, and the compound represented by the following chemical formula 1 is added in order to have an appropriate dissolution rate for a photoresist and to adjust the polarity of the composition so as to reduce the peak height.

[ chemical formula 1 ]

In the chemical formula 1, R₁Is C1-C4 alkyl, R₂Is C2-C4 alkyl. Preferably, said R is₁Is C2-C4 alkyl.

According to an embodiment, at least one selected from the group consisting of ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, ethyl 3-ethoxypropionate, propyl 3-ethoxypropionate, butyl 3-ethoxypropionate, ethyl 3-propoxypropionate, propyl 3-propoxypropionate, butyl 3-propoxypropionate, ethyl 3-butoxypropionate, propyl 3-butoxypropionate, and butyl 3-butoxypropionate, represented by the chemical formula 1, preferably ethyl 3-ethoxypropionate.

Specifically, the ethyl 3-ethoxypropionate is a non-acetate compound, and a polyhydroxystyrene/acrylic copolymer partially substituted with a resin, a sensitizer, and a protective group, which are main components of a resist such as ArF, KrF, EUV, etc., has an appropriate dissolution rate, thereby leaving a residue on the wafer surface. The ethyl 3-ethoxypropionate had a lower polarity (calculated solubility parameter polarity: 5.7 MPa)^1/2) The diluent is used to adjust the polarity of the diluent composition so that the swelling (swelling) speed of the PR toward the center of the wafer at the EBR end is reduced by the diluent, and the peak height (Hump height) is reduced, thereby increasing the usable area, reducing the defect rate due to Hump (Hump) in the subsequent process, and contributing to the improvement of productivity.

The content of the compound represented by the chemical formula 1 is preferably 5 to 30% by weight relative to the total weight of the thinner composition of the present invention, and when the content satisfies the above range, an excellent hump reducing effect and EBR characteristics can be provided.

However, when exceeding the range, the hump reducing effect is insufficient or the dissolving ability is lowered and the EBR characteristics are lowered.

In addition, R of the chemical formula 1₂Is C1 alkyl (methyl), has a higher polarity than other propionate compounds, e.g., methyl 3-methoxypropionate having a structure similar to that of ethyl 3-ethoxypropionate has a relatively higher polarity (calculated polarity of solubility parameter: 6.7 MPa)^1/2) Relatively greater amounts are therefore required to reduce the polarity of the diluent composition and lead to non-uniformity of the PR coating due to having a high volatility. Thus, methyl 3-methoxypropionate is preferably not contained in the present invention.

In addition, esters or ester salts such as butyl acetate, amides, aromatic hydrocarbons, and the like cannot achieve linearity of EBR lines with respect to photosensitive films after the EBR (edge Bead remove) step, or cannot achieve an effect of reducing peak heights (Hump height) even if linearity is achieved. Thus, the diluent composition according to the present invention preferably does not contain compounds such as esters or ester salts such as butyl acetate, amides, aromatic hydrocarbons and the like.

d) The calculated value of the solubility parameter was 7MPa^1/2～8MPa^1/2Of (2) a solvent

The diluent composition of the invention also comprises a calculated polarity of solubility parameter of 7MPa^1/2～8MPa^1/2The solvent of (1). Since the inclusion of the solvent increases the polarity of the thinner composition, the dissolution rate of the photoresist such as ArF, KrF, EUV, etc. is increased to improve the EBR characteristics. However, in order to increase the polarity of the diluent composition, gamma-butyrolactone (16.0 MPa) is added^1/2) Solvents having a higher polarity than cyclopentanone may cause attack (attack) on the photoresist, and thus, it is preferable in the present invention that gamma-butyrolactone is not included.

The calculated value of the solubility parameter is 7MPa^1/2～8MPa^1/2The solvent (C) is preferably selected from ethyl lactate (7.6 MPa)^1/2) Propylene glycol monomethyl ether (7.5 MPa)^1/2) And methyl 2-hydroxyisobutyrate (7.2 MPa)^1/2) At least one of the group consisting of a calculated polarity value of the solubility parameter of 7MPa^1/2～8MPa^1/2The content of the solvent (C) is not limited, but it is preferable that the solubility parameter is contained in a calculated polarity value of 7MPa with respect to 100 wt% of the total of the C2-C4 alkylene glycol C1-C4 alkyl ether acetates^1/2～8MPa^1/2The content of the solvent (b) is 50 to 100% by weight.

In addition, in order to further improve the effect of the thinner composition of the present invention, usual additives may be contained in addition to the above components.

< photosensitive resin and method for removing antireflection film >

The invention includes a photosensitive resin removing method, an antireflection film removing method, and a photosensitive resin and antireflection film removing method.

The method for removing a photosensitive resin and/or an antireflection film of the present invention uses the thinner composition of the present invention.

According to one embodiment, the method for removing the photosensitive resin of the present invention comprises: a step of forming a photosensitive resin on a substrate; and a step of removing the photosensitive resin with the diluent composition. In the photosensitive resin removing method of the present invention, the photosensitive resin removing step includes: partially removing the photosensitive resin formed on the substrate.

The method for removing an antireflection film of the present invention includes: a step of forming an antireflection film on a substrate; and a step of removing the antireflection film by using the thinner composition. In the method for removing an antireflection film of the present invention, the antireflection film removing step includes: partially removing the anti-reflection film formed on the substrate.

The photosensitive resin and the method for removing the antireflection film of the present invention include: a step of forming a photosensitive resin on a substrate; forming an antireflection film on the photosensitive resin; and a step of removing the photosensitive resin and the antireflection film with the thinner composition, or comprises: a step of forming an antireflection film on a substrate; forming a photosensitive resin on the antireflection film; and a step of removing the photosensitive resin and the antireflection film with the diluent composition. In the photosensitive resin and antireflection film removing method of the present invention, the photosensitive resin and antireflection film removing step includes: and partially removing the photosensitive resin and the anti-reflection film formed on the substrate.

In the method for removing the photosensitive resin and/or the antireflection film, a known method can be applied to the step of forming the photosensitive resin and/or the antireflection film on the substrate. The content of the diluent composition is also applicable to the method for removing the photosensitive resin and/or the antireflection film.

The present invention will be described in more detail below with reference to examples. However, the following examples are intended to be more specifically illustrative, and the scope of the present invention is not limited by the following examples.

Examples 1 to 12 and comparative examples 1 to 18: preparation of Diluent composition

The diluent compositions of examples 1 to 12 and comparative examples 1 to 18 were prepared by adding the components in the following weight% as shown in tables 1 and 2 to a mixing tank equipped with a stirrer, and then stirring at 500rpm for 1 hour at normal temperature.

[ TABLE 1 ]

[ TABLE 2 ]

a) Acetic acid ester

Propylene glycol monomethyl ether acetate

b) Cyclic ketones

B-1: cyclopentanone

B-2: cyclohexanone

c) Propionic acid ester

C-1: 3-Ethoxypropionic acid ethyl ester (Compound of the following chemical formula 1-1)

[ chemical formula 1-1 ]

C-2: 3-Methoxypropionic acid Ethyl ester (Compound of the following chemical formula 1-2)

[ chemical formula 1-2 ]

C-3: 3-Methoxypropionic acid methyl ester (Compound of the following chemical formula 1-3)

[ chemical formula 1-3 ]

d) The calculated value of the solubility parameter was 7MPa^1/2～8MPa^1/2Of (2) a solvent

D-1: ethyl lactate (7.6 MPa)^1/2)

D-2: propylene glycol monomethyl ether (7.5 MPa)^1/2)

D-3: 2-Hydroxyisobutyric acid methyl ester (7.2 MPa)^1/2)

e) Other solvents

E-1: gamma-butyrolactone (16.0 MPa)^1/2)

E-2: acetic acid n-butyl ester

E-3: propylpropionate

E-4: n, N-dimethylformamide

E-5: n-methyl-2-pyrrolidone

E-6: dimethyl sulfoxide

E-7: 1,2, 4-trimethylbenzene

E-8: cumene (isopropyl benzene)

E-9: methyl ethyl ketone

E-10: methyl amyl ketone

Experimental example: evaluation of characteristics of Diluent composition

The thinner compositions according to examples and comparative examples were evaluated for characteristics using 4 kinds of Photoresists (PR) of the following table 3.

[ TABLE 3 ]

Distinguishing	Class of PR
		PR 1	Krf PR for Implanter
PR 2	PR A for EUV
		PR 3	PR B for EUV
PR 4	PR C for EUV

Experimental example 1: EBR (edge Bead Removal) test

On an 8-inch silicon oxide substrate, PR was applied to the entire surface of the wafer using the photosensitive resin composition shown in table 2 under the evaluation conditions shown in table 4, and an EBR test for removing unnecessary photosensitive films at the edge portions was performed using the thinner compositions of examples 1 to 12 and comparative examples 1 to 18 under the evaluation conditions shown in table 4.

The EBR test was performed for 4 kinds of PR, and the diluent compositions of examples 1 to 12 and comparative examples 1 to 18 were supplied from a pressure tank provided with a pressure gauge at a constant pressure, and the diluent injected at the constant pressure was evaluated under the condition that the total injection amount was 1.5CC in the EBR process. The completed substrates were evaluated by optical microscopy at 400 and 1000 magnifications to determine linearity, uniformity and tailing (tailing) phenomenon of the EBR lines, and the results thereof are shown in the following tables 6 and 7.

Further, for the evaluation samples showing the linearity and uniformity of the EBR line, the film thicknesses of 25 μ M on the inner side and 25 μ M on the outer side of the wafer were measured with respect to the EBR line of the photosensitive film by a film thickness meter (Dektak 6M, Veeco) to derive the maximum film thickness value, and then the peak heights were calculated excluding the average thickness of the photosensitive film, and the results thereof are shown in the following tables 6 and 7 (refer to fig. 1).

[ TABLE 4 ]

Experimental example 2: RRC (reducing Resist coating) test

The diluent compositions of examples 1 to 12 and comparative examples 1 to 18 were used to perform RRC performance tests on the 4 photoresists of Table 2. As shown in table 5, before coating a photoresist on an 8-inch silicon oxide wafer, 2.0cc of each thinner composition was coated, the thinner was dispensed over the entire upper surface of the wafer by rotating the substrate at 500rpm for 4 seconds, and 4 kinds of PR were coated with 0.5 and 0.3cc to perform an RRC process for measuring the coating distribution and consumption amount of the photoresist based on the thinner, and the results are shown in the following tables 6 and 7.

[ TABLE 5 ]

EBR and RRC test results

[ TABLE 6 ]

[ TABLE 7 ]

< EBR evaluation criteria >

X: a state in which there is no uniformity of EBR lines to the photosensitive film after EBR and tailing phenomenon occurs (refer to FIG. 2a)

Delta: case where there is no linearity and uniformity of EBR line to photosensitive film after EBR (refer to FIG. 2b)

O. the case where there is linearity of EBR line to the photosensitive film after EBR but there is no uniformity (refer to FIG. 2c)

Very good linearity and uniformity of EBR line to photosensitive film after EBR (refer to FIG. 2d)

< Standard of Peak height results >

Cases where there is no line uniformity after EBR and therefore no representative measurement can be made

X peak height

The above situation

Peak height of delta

In the case of

Peak height of

In the case of

Very good peak height

The following cases

< criteria for RRC evaluation >

RRC results coating of photosensitive film on wafer 80% or less (refer to FIG. 3a)

Results of RRC testing 80% to 95% of the photosensitive film was coated on the wafer (see FIG. 3b)

RRC results indicate that the photosensitive film on the wafer was coated by 95% or more, but there was a stain or uncoated portion (see FIG. 3c)

RRC results shows that 95% or more of the photosensitive film was coated on the wafer and that no stain was observed (see FIG. 3d)

Evaluation 1: EBR and Peak height evaluation of Diluent compositions

Referring to the above table 6 and table 7, the thinner compositions according to examples 1 to 12 of the present invention exhibited excellent EBR characteristics and low peak heights for all photosensitive films. In particular, the calculated value of the polarity compared to the non-parameter-containing value is 7MPa^1/2～8MPa^1/2The thinner compositions of examples 1 to 4 and 12 of the solvent of (1), and the thinner compositions of examples 5 to 11 additionally comprising the solvent show more excellent EBR characteristics and also reduced peak heights.

In contrast, the compositions described in comparative examples 1, 3 and 9, which did not contain cyclopentanone, did not ensure linearity and uniformity of the EBR line; the cases of comparative examples 2,4 to 8, and 10 to 18, which include cyclopentanone but not the propionate compound represented by chemical formula 1 according to the present invention, result in an increase in peak height and a decrease in linearity and uniformity of the EBR line.

Evaluation 2: RRC evaluation of Diluent compositions

Referring to said table 6 and table 7, the thinner compositions according to examples 1 to 12 of the present invention showed excellent RRC performance for all photosensitive films. On the contrary, it was confirmed that the thinner compositions of comparative examples 1 to 18 had reduced coatability to part of PR. Thus, the thinner composition according to the present invention may not only exhibit effects on a specific photosensitive film but also provide excellent removal performance for various photosensitive films.

Claims (10)

1. A diluent composition characterized by:

comprises the following steps: a) C2-C4 alkylene glycol C1-C4 alkyl ether acetate; b) cyclopentanone; c) a compound represented by the following chemical formula 1:

[ chemical formula 1 ]

In the chemical formula 1, R₁Is C1-C4 alkyl, R₂Is C2-C4 alkyl.

2. The diluent composition according to claim 1, characterized in that:

the compound represented by the chemical formula 1 is ethyl 3-ethoxypropionate.

3. The diluent composition according to claim 1, characterized in that:

the C2-C4 alkylene glycol C1-C4 alkyl ether acetate in the a) is at least one selected from the group consisting of propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate and ethylene glycol monoethyl ether acetate.

4. The diluent composition according to claim 1, characterized in that:

the content of the C2-C4 alkylene glycol C1-C4 alkyl ether acetate in the a) is 30-80 wt% relative to the total weight of the composition; the content of cyclopentanone in b) is 10 to 50 wt%; the content of the compound represented by the chemical formula 1 in c) is 5 to 30% by weight.

5. The diluent composition according to claim 1, characterized in that:

the diluent composition also comprises a calculated polarity value of a solubility parameter of 7MPa^1/2～8MPa^1/2The solvent of (1).

6. The diluent composition according to claim 5, characterized in that:

the calculated value of the solubility parameter is 7MPa^1/2～8MPa^1/2The solvent (b) is at least one selected from the group consisting of ethyl lactate, propylene glycol monomethyl ether and methyl 2-hydroxyisobutyrate.

7. The diluent composition according to claim 1, characterized in that:

the thinner composition is used for removing at least one of a photosensitive resin and an antireflection film.

8. The diluent composition according to claim 7, characterized in that:

the photosensitive resin is at least one of ArF, KrF and EUV photoresist.

9. A method for removing a photosensitive resin, comprising:

a step of forming a photosensitive resin on a substrate; and

a step of removing the photosensitive resin with the thinner composition according to any one of claims 1 to 8.

10. A method for removing an antireflection film, comprising:

a step of forming an antireflection film on a substrate; and

a step of removing the antireflection film by using the thinner composition according to any one of claims 1 to 8.

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