KR102128374B1 - Thinner composition for improving coating and removing performance of resist - Google Patents

Abstract

The present invention comprises at least one compound of propylene glycol alkyl (1 to 10 carbon atoms) ether acetate and alkyl (1 to 10 carbon atoms) alkoxy (1 to 10 carbon atoms) propionate and a ketone having 1 to 10 carbon atoms, By using a photoresist or SOH, the photoresist can be evenly applied to the entire surface of the substrate, reducing the amount of photoresist used to improve process cost and productivity, and removing unnecessary photoresist after photoresist application is excellent. It relates to a thinner composition and a substrate processing method using the same.

Description

Thinner composition for improving and removing resist coating properties{THINNER COMPOSITION FOR IMPROVING COATING AND REMOVING PERFORMANCE OF RESIST}

The present invention relates to a thinner composition for improving and removing resist coating properties.

Fine circuit patterns, such as semiconductor integrated circuits, are uniformly coated with a photoresist containing a photosensitive compound and a solvent, such as a conductive metal film or an oxide film formed on a substrate by rotational coating, and then subjected to exposure, development, etching and peeling processes. It is manufactured through a method of implementing a desired microcircuit pattern. At this time, the subsequent exposure process is implemented by a method of finely exposing a desired pattern to the coating film using light of a short wavelength in the ultraviolet region, and thus is very sensitive to external and internal contamination. Therefore, unnecessary photoresist residues and other contaminants applied to the edge or back of the substrate in the application process must be removed because they can become a fatal source of contamination in the subsequent exposure process. In order to remove such contaminants, thinner compositions have been used in EBR (edge bead removing) processes.

Conventionally, as a thinner composition for removing photoresist, a single solvent such as ethylcellosolve acetate (ECA), methylmethoxy propionate (MMP) and ethyl lactate (EL) is widely used. Although used, ethyl cellosolve acetate has problems in its use due to its toxicity to the human body, and methylmethoxypropionate and ethyl lactate due to economic and performance limitations.

In order to solve this problem, a method of mixing and using conventional single solvents has been developed, and such a thinner composition in the form of a mixture is a mixture of propylene glycol alkyl ether propionate and methyl ethyl ketone, or propylene glycol alkyl ether. Mixture of cypionate and butyl acetate (Japanese Patent Publication No. Hei 7-160008); A mixture of ethyl lactate and propylene glycol alkyl ether (US Pat. No. 4,886,728) is known.

On the other hand, in recent years, as semiconductor integration increases, photoresist using short-wavelength KrF and ArF (including ArF immersion) light sources has been applied, and as the effect of the use of photoresist on the integrated circuit manufacturing cost significantly increases, cost reduction is achieved. In order to reduce the amount of photoresist used, there has been a continuous demand.

Due to these demands, RRC (photoresist reduction, reducing resist consumption) allows the photoresist to be evenly applied to the entire surface of the substrate by using only a small amount of photoresist by first treating the surface of the substrate with a treatment composition before applying the photoresist. ) Process has been applied. As the diameter of the substrate (wafer) increases along with an increase in the degree of integration, the importance of the RRC process is further increased, and thus it is required to develop a treatment composition having a high RRC efficiency while sufficiently performing the existing EBR process.

Currently, the photoresist residue removal process and the photoresist coating treatment process are separate processes, and the thinner composition used in the residue removal process and the photoresist coating treatment composition are each used in separate compositions.

Patent Document 1: Japanese Patent Publication No. Hei 7-160008 Patent Document 2: U.S. Registered Patent No. 4,886,728

An object of the present invention is to provide a thinner composition that can be used simultaneously in the RRC process as well as the EBR process.

In addition, another object of the present invention is to provide a substrate processing method using the thinner composition.

1.Resist coatability comprising at least one compound of propylene glycol alkyl (1 to 10 carbon atoms) ether acetate and alkyl (1 to 10 carbon atoms) alkoxy (1 to 10 carbon atoms) propionate and ketone having 1 to 10 carbon atoms Thinner composition for improvement and removal.

2. In the above 1, wherein the propylene glycol alkyl ether acetate is at least one selected from the group consisting of propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate and propylene glycol butyl ether acetate, improving resist coatability Thinner composition for use and removal.

3. In the above 1, wherein the alkyl alkoxy propionate is methyl 3-methoxy propionate, methyl 3-ethoxy propionate, methyl 4-methoxy propionate, methyl 4-ethoxy propionate, At least one member selected from the group consisting of ethyl 3-methoxy propionate, ethyl 3-ethoxy propionate, ethyl 4-methoxy propionate and ethyl 4-ethoxy propionate, for improving resist coatability and Thinner composition for removal.

4. In the above 1, the ketone is acetone, methyl ethyl ketone, methyl propyl ketone, methyl butyl ketone, methyl pentyl ketone, methyl hexyl ketone, methyl heptyl ketone, methyl octyl ketone, ethyl propyl ketone, ethyl butyl ketone and ethyl pentyl A thinner composition for improving and removing resist coating properties, which is at least one selected from the group consisting of ketones.

5. In the above 1, the mixed weight ratio of the propylene glycol alkyl ether acetate and the ketone is 10:90 to 90:10, thinner composition for improving and removing resist coating properties.

6. In the above 1, the mixed weight ratio of the alkyl alkoxy propionate and the ketone is 10:90 to 90:10, thinner composition for improving and removing resist coating properties.

7. A substrate treatment method comprising the steps of modifying a substrate with the thinner composition of any one of 1 to 6 above and applying SOH to the modified substrate.

8. In the above 7, the SOH applied in the coating step is at least one of C-SOH and Si-SOH, the substrate processing method.

9. The method of 7 above, further comprising treating the substrate with the thinner composition after the SOH application step.

10. The method of 9 above, further comprising the step of applying a photoresist after treating the thinner composition of the SOH-coated substrate and treating the thinner composition again.

The thinner composition of the present invention can evenly use a small amount of photoresist or SOH so that the photoresist is evenly applied to the entire surface of the substrate, thereby reducing the amount of photoresist used and improving process cost and productivity.

The thinner composition of the present invention can be quickly and effectively removed unnecessary photoresist and SOH by spraying on the edge portion and the back portion of the substrate.

The thinner composition of the present invention has excellent solubility in various photoresist films, SOH layers, lower antireflection films (BARC) and underlayers.

The thinner composition of the present invention has excellent solubility in the main components of the photoresist and antireflection film having a high polarity structure, and thus, after the EBR process, the wafer lower cleaning process, and the pretreatment process on the upper portion of the wafer before photoresist application, the coater It does not pollute the cup holder or block the outlet.

FIG. 1 shows a case where a thinner composition 0.5cc is applied on an 8-inch wafer and a photoresist is applied, so that photoresist is applied 99 to 100% or more on the wafer.
FIG. 2 shows a case where 0.5 cc of thinner composition is applied on an 8-inch wafer and a photoresist is applied, so that the photoresist is less than 95% applied on the wafer.
Figure 3 shows the evaluation point of the coating uniformity according to the type of photoresist applied on the wafer.

The present invention comprises at least one compound of propylene glycol alkyl (1 to 10 carbon atoms) ether acetate and alkyl (1 to 10 carbon atoms) alkoxy (1 to 10 carbon atoms) propionate and a ketone having 1 to 10 carbon atoms, By using a photoresist or SOH, the photoresist can be evenly applied to the entire surface of the substrate, reducing the amount of photoresist or SOH used to improve process cost and productivity, and removing unnecessary photoresist after photoresist application It relates to this excellent thinner composition and a substrate processing method using the same.

Hereinafter, the present invention will be described in detail.

<thinner composition>

The thinner composition for improving and removing resist coating properties of the present invention comprises at least one compound and carbon number of propylene glycol alkyl (1 to 10 carbon atoms) ether acetate and alkyl (1 to 10 carbon atoms) alkoxy (1 to 10 carbon atoms) propionate 1 to 10 ketones.

In the present invention, the resist is a concept including a hardmask material and a BARC (lower anti-reflection film) material in addition to the general photoresist material, and includes, for example, S0H (Spin-on-Hardmask).

In addition, in the present invention, (carbon number n to m) means the number of carbon atoms of the substituent described before the parentheses.

The ketone having 1 to 10 carbon atoms used in the present invention is a component that maximizes EBR process characteristics and RRC effect by imparting appropriate volatility and surface tension of the composition.

If the ketone is a ketone having 1 to 10 carbon atoms, the type is not particularly limited, for example, acetone, methyl ethyl ketone, methyl propyl ketone, methyl butyl ketone, methyl pentyl ketone, methyl hexyl ketone, methyl heptyl ketone, methyl octyl Ketone, ethyl propyl ketone, ethyl butyl ketone, ethyl pentyl ketone, and the like. These may be used alone or in combination of two or more.

The content of the ketone is not particularly limited within a range capable of functioning, for example, may be included in 10 to 90% by weight of the total weight of the composition, preferably 10 to 50% by weight, more preferably It is preferable that it is 10 to 30% by weight. When included in 10 to 90% by weight, the composition has an appropriate volatility, so that the tailing phenomenon does not occur in the edge bead removal (EBR) process of the edge portion, and the removal process can be effectively performed, and the coating uniformity It can maintain excellent, and can maximize the effect of reducing resist consumption (RRC) that can apply a wafer with a small amount of photoresist and SOH.

The propylene glycol alkyl (1 to 10 carbon atoms) ether acetate used in the present invention is a component that is used together with a ketone having 1 to 10 carbon atoms to significantly improve EBR process properties and RRC effects.

The type of the propylene glycol alkyl (1 to 10 carbon atoms) ether acetate is not particularly limited, for example, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, propylene glycol butyl ether acetate, etc. These may be used alone or in combination of two or more.

The content of the propylene glycol alkyl (1 to 10 carbon atoms) ether acetate is not particularly limited within a range capable of functioning, for example, may be included in 10 to 90% by weight of the total weight of the mixture with ketone, Preferably it is 30 to 90% by weight. When included in 10 to 90% by weight, the tailing phenomenon does not occur in an unnecessary photoresist film removal process (Edge Bead Removing, EBR) of the edge portion, the removal process can be effectively performed, the coating uniformity can be maintained excellently, and less It is possible to maximize a reducing resist consumption (RRC) effect that can apply a wafer with positive photoresist and SOH.

The alkyl (carbon number 1 to 10) alkoxy (carbon number 1 to 10) propionate used in the present invention is a component that is used in combination with a ketone having 1 to 10 carbon atoms to significantly improve EBR process properties and RRC effects.

The type of the alkyl (1 to 10 carbon atoms) alkoxy (1 to 10 carbon atoms) propionate is not particularly limited, for example, methyl 3-methoxy propionate, methyl 3-ethoxy propionate, methyl 4 -Methoxy propionate, methyl 4-ethoxy propionate, ethyl 3-methoxy propionate, ethyl 3-ethoxy propionate, ethyl 4-methoxy propionate, ethyl 4-ethoxy propionate Nate etc. are mentioned, These can be used individually or in mixture of 2 or more types.

The content of the alkyl (carbon number 1 to 10) alkoxy (carbon number 1 to 10) propionate is not particularly limited within a range capable of functioning, for example, 10 to 90 weight of the total weight of the mixture with ketone It may be included in %, preferably 30 to 90% by weight. When included in 10 to 90% by weight, the tailing phenomenon does not occur in an unnecessary photoresist film removal process (Edge Bead Removing, EBR) of the edge portion, the removal process can be effectively performed, the coating uniformity can be maintained excellently, and less It is possible to maximize the effect of reducing resist consumption (RRC) to apply the wafer with positive photoresist and SOH.

In addition, when the thinner composition of the present invention includes the above compounds at the same time, propylene glycol alkyl (1 to 10 carbon atoms) 10 to 90 parts by weight of ether acetate, alkyl (1 to 10 carbon atoms) alkoxy (1 to 10 carbon atoms) propionate 10 to 90 parts by weight, may be included as 10 to 90 parts by weight of ketone having 1 to 10 carbon atoms, preferably propylene glycol alkyl (1 to 10 carbon atoms) ether acetate 30 to 90 parts by weight, alkyl (1 to 10 carbon atoms) alkoxy ( It is preferable that it is 30 to 90 parts by weight of propionate and 10 to 70 parts by weight of ketone having 1 to 10 carbon atoms.

Optionally, the thinner composition of the present invention may further include a solvent used in the art to the extent that it does not depart from the object of the present invention. For example, propylene glycol alkyl ether propionate, alkyl lactate, propylene glycol alkyl ether, etc. are mentioned, and these can be used individually or in mixture of 2 or more types.

Optionally, the thinner composition of the present invention may further add a conventional additive in addition to the aforementioned components, and a surfactant as an additive. pH adjusting agents and the like can be used.

In addition, the additive is not limited to this, and to further improve the effect of the present invention, various other additives known in the art may be selected and added.

The thinner composition for improving and removing resist coating properties including the above components has excellent solubility for various photoresist films, SOH films, lower antireflection films (BARC) and underlayers, EBR properties, rework properties and photos The coating performance of the resist can be improved.

Particularly, in the case of i-line, KrF, and ArF photoresist, since the basic structure of the photosensitive resin is different, it is necessary to adjust the composition content of the organic solvent to improve the solubility and coating properties of all of them. The thinner composition satisfies this.

<Substrate treatment method>

In addition, the present invention provides a substrate processing method using the thinner composition according to the present invention.

The substrate processing method of the present invention includes the step of modifying the substrate with the thinner composition and applying SOH to the modified substrate.

The substrate modification step of the present invention is performed before applying the spin-on-hardmask (SOH), so that the removal process can be effectively performed without generating a tailing phenomenon in the edge bead removing (EBR) process of the edge region. In addition, it is possible to maintain excellent coating uniformity and maximize the effect of reducing resist consumption (RRC) that can apply a wafer with a small amount of SOH.

The modifying step may be performed by applying the thinner composition according to the present invention by a conventional method, for example, by spraying a thinner composition in the center of a fixed substrate, and then rotating the substrate to spray the thinner composition on the front surface of the substrate. It can be spread, and the injection amount may be 0.1cc to 2cc, preferably 0.1cc to 1cc.

The step of applying the spin-on-hardmask (SOH) of the present invention is for forming a solid pattern, and when using as a mask using only photoresist, the height/aspect rate is increased or used as a hard mask This is to solve a problem that is not hard enough.

SOH used in the coating step, SOH may be at least one of C-SOH and Si-SOH. When C-SOH is used, stability at high temperature is excellent, and when Si-SOH is used, control of optical properties is easy.

The substrate processing step of the present invention may further include a step of treating the substrate with a thinner composition according to the present invention after the step of applying the SOH.

By treating the substrate with a thinner composition after the step of applying the SOH, it is possible to quickly and effectively remove unnecessary SOH applied to the edge or back of the substrate before the exposure process, and thereafter, less in the step of applying the photoresist By allowing the wafer to be coated with a positive amount of photoresist, process cost and productivity can be improved.

The substrate processing step of the present invention may further include applying a photoresist after treating the thinner composition of the SOH coated substrate, and then treating the thinner composition again.

By applying the photoresist in the above step, and then treating the substrate again with a thinner composition, it is possible to quickly and effectively remove unnecessary photoresist and SOH applied to the edge or back of the substrate before the exposure process.

Hereinafter, preferred embodiments are provided to help the understanding of the present invention, but these examples are merely illustrative of the present invention and do not limit the scope of the appended claims, and the embodiments are within the scope and technical scope of the present invention. It is apparent to those skilled in the art that various changes and modifications to the present invention are possible, and it is natural that such modifications and modifications fall within the scope of the appended claims.

Example And Comparative example

After adding the components and composition ratios shown in Table 1 to the mixing tank equipped with a stirrer, the mixture was stirred at a rate of 500 rpm for 1 hour at room temperature to prepare a thinner composition.

division
(weight%) Ketone Propylene glycol
Alkyl ether
acetate Alkyl alkoxy
Propionate Polyalkylene
Glycol Alkyl
ester ingredient content ingredient content ingredient content ingredient content ingredient content Example 1 A-1 15 B-1 85 - - - - - - Example 2 A-1 35 B-1 65 - - - - - - Example 3 A-1 65 B-1 45 - - - - - - Example 4 A-1 85 B-1 25 - - - - - - Example 5 A-1 35 B-2 65 - - - - - - Example 6 A-1 35 B-3 65 - - - - - - Example 7 A-1 15 - - C-1 85 - - - - Example 8 A-1 35 - - C-1 65 - - - - Example 9 A-1 65 - - C-1 45 - - - - Example 10 A-1 85 - - C-1 25 - - - - Example 11 A-1 35 - - C-2 65 - - - - Example 12 A-1 35 - - C-3 65 - - - - Example 13 A-2 40 B-1 60 - - - - - - Example 14 A-2 50 B-1 50 - - - - - - Example 15 A-3 40 - - C-1 60 - - - - Example 16 A-3 50 - - C-1 50 - - - - Example 17 A-1 20 B-1 40 C-1 40 - - - - Comparative Example 1 A-1 100 - - - - Comparative Example 2 B-1 100 - - - - Comparative Example 3 C-1 100 - - - - Comparative Example 4 B-1 60 D-1 30 E-1 10 Comparative Example 5 C-1 50 D-1 30 E-1 20 Comparative Example 6 C-1 50 D-2 30 E-2 20 A-1: methyl pentyl ketone
A-2: methyl ethyl ketone
A-3: methyl octyl ketone
B-1: Propylene glycol methyl ether acetate
B-2: Propylene glycol ethyl ether acetate
B-3: Propylene glycol butyl ether acetate
C-1: Ethyl 3-ethoxy propionate
C-2: methyl 3-ethoxy propionate
C-3: ethyl 3-methoxy propionate
D-1: polyethylene glycol (molecular weight 200)
D-2: Polypropylene glycol (molecular weight 300)
E-1: methyl lactate
E-2: ethyl lactate

Test Methods

One. RRC ( reducing resist coating ) Performance evaluation

The RRC performance for the four Photoresist, Spin-on-Hardmask (SOH) and BARC of Table 2 were tested using the thinner compositions of Examples and Comparative Examples. According to the recipe shown in Table 3, after applying each thinner composition before applying 6 types of PR on an 8-inch silicon oxide substrate, an RRC process was performed to measure the distribution and consumption of photoresist according to the thinner composition. In the case of BARC, an RRC process was performed using each thinner composition without heat treatment. Table 4 shows the results of photoresist consumption after applying 0.5 cc of thinner composition on an 8 inch wafer, 1.0 cc for PR1 to 4 and SOH, and 0.4 cc for BARC, respectively.

<Evaluation criteria>

◎: When photoresist was applied 99 to 100% on a wafer

○: 97 to 98% of photoresist was applied on the wafer

△: When photoresist was applied 85 to 90% on the wafer

X: When photoresist is less than 85% applied on the wafer

division PR type PR 1 PR for i-line PR 2 PR for KrF PR 3 PR for ArF PR 4 PR for ArF-immersion SOH Resin for SOH BARC BARC for ArF

step Time(sec) Speed (rpm) Accelerator (rpm/sec) Dispensing (cc) One 2.5 0 10,000 0.5(Thinner) 2 1.5 900 10,000 0 3 9.5 1500 10,000 0 4 5.0 600 10,000 0.5~1(PR) 5 5.0 1500 10,000 0 6 10.0 1000 10,000 0

When the application conditions were described with reference to Table 3, 0.5 cc of thinner composition was sprayed onto the substrate for 2.5 seconds as a first step. In the second step, the substrate was rotated so that the thinner composition spread over the wafer for 1.5 seconds. In the third step, the substrate was rotated for 9.5 seconds. In the fourth step, the substrate was relatively rotated while spraying the photoresist, SOH and BARC, and the photoresist, SOH and BARC sprayed on the substrate were entirely coated. The substrate was rotated for 5 seconds in the fifth step and 10 seconds in the sixth step.

division SOH(1.0cc) PR1(1.0cc) PR2(1.0cc) PR3(1.0cc) PR4(1.0cc) BARC(0.4cc) Example 1 ◎ ◎ ◎ ◎ ◎ ◎ Example 2 ◎ ◎ ◎ ◎ ◎ ◎ Example 3 ◎ ◎ ○ ◎ ◎ ◎ Example 4 ◎ ◎ ○ ◎ ◎ ◎ Example 5 ◎ ○ ○ ◎ ◎ ◎ Example 6 ◎ ○ ○ ◎ ◎ ◎ Example 7 ◎ ◎ ◎ ◎ ◎ ◎ Example 8 ◎ ◎ ◎ ◎ ◎ ◎ Example 9 ◎ ◎ ◎ ◎ ◎ ◎ Example 10 ◎ ◎ ○ ◎ ◎ ◎ Example 11 ◎ ○ ○ ◎ ◎ ◎ Example 12 ◎ ○ ○ ◎ ◎ ◎ Example 13 ◎ ○ ○ ◎ ◎ ◎ Example 14 ○ ○ ○ ○ ◎ ◎ Example 15 ○ ○ ◎ ◎ ○ ◎ Example 16 ○ ○ ○ ○ ◎ ○ Example 17 ○ ○ △ ○ ○ ○ Comparative Example 1 X X X X X X Comparative Example 2 X X X X X X Comparative Example 3 X X X X X X Comparative Example 4 X X X X X △ Comparative Example 5 △ △ X △ △ △ Comparative Example 6 △ △ X △ △ △

Referring to Table 4, the thinner compositions of the Examples according to the present invention show excellent RRC performance for all photosensitive films. On the other hand, in the comparative example, it was confirmed that the coating performance of the photoresist, SOH, and BARC was significantly lower than that of the example.

In addition, the thinner compositions of the Examples according to the present invention maintained equally excellent shape even when changing the rotational speed (rpm) condition of the RRC. This means that the thinner composition according to the present invention does not show an effect only in a specific condition, but exhibits the same performance in various conditions, and is more stable than a conventional thinner composition against changes in process conditions.

2. EBR ( Edge Bead Removing ) Performance evaluation

After applying the photosensitive resin composition shown in Table 2 to an 8 inch silicon oxide substrate, EBR for removing the unnecessary photosensitive film at the edge region under the conditions described in Table 5 for the thinner compositions of Examples and Comparative Examples The experiment was conducted. The thinner compositions of each Example and Comparative Example were supplied from a pressure vessel equipped with a pressure gauge, and the pressure at this time was 1 kgf, and the flow rate of the thinner composition from the EBR nozzle was 10 to 30 cc/min. And the removal performance of the unnecessary photosensitive film was evaluated using an optical microscope, and the results are shown in Table 6 below.

<Evaluation criteria>

◎: EBR line uniformity for the photosensitive film after EBR is constant

○: EBR line uniformity with respect to the photosensitive film after EBR is 75% or more.

△: After EBR, the shape of the edge part is distorted due to the thinner dissolving action.

X: Tailing occurs in the membrane at the edge after EBR

division Rotation speed (rpm) Time (Sec) Dispense conditions 300~2000 7 Spin coating Adjustable according to the thickness of the photosensitive film 15 EBR condition 1 2000 20 EBR condition 2 2000 25 Drying conditions 1300 6

division SOH(1.0cc) PR1(1.0cc) PR2(1.0cc) PR3(1.0cc) PR4(1.0cc) BARC(0.4cc) Example 1 ◎ ◎ ◎ ◎ ◎ ◎ Example 2 ◎ ◎ ◎ ◎ ◎ ◎ Example 3 ◎ ◎ ◎ ◎ ◎ ◎ Example 4 ◎ ○ ○ ○ ◎ ○ Example 5 ◎ ○ ○ ○ ◎ ◎ Example 6 ◎ ○ ○ ○ ◎ ◎ Example 7 ◎ ◎ ◎ ◎ ◎ ◎ Example 8 ◎ ◎ ◎ ◎ ◎ ◎ Example 9 ◎ ◎ ◎ ◎ ◎ ◎ Example 10 ◎ ○ ○ ○ ◎ ○ Example 11 ◎ ○ ○ ○ ◎ ◎ Example 12 ◎ ○ ○ ○ ◎ ◎ Example 13 ○ ◎ ○ ◎ ◎ ◎ Example 14 ○ ○ ○ ○ ○ ◎ Example 15 ◎ ○ ○ ◎ ◎ ◎ Example 16 ○ ○ ○ ○ ◎ ○ Example 17 ○ △ △ ○ ○ ○ Comparative Example 1 X X X X X X Comparative Example 2 X X X X X X Comparative Example 3 X X X X X X Comparative Example 4 X X X X X X Comparative Example 5 △ X X △ X △ Comparative Example 6 △ △ X △ △ △

Referring to Table 6, the thinner compositions of the Examples according to the present invention show excellent EBR performance for all photosensitive films. Therefore, it can be considered that all four types of photoresist, SOH, and EBR performance of the lower antireflection film (BARC) are satisfied.

On the other hand, it can be seen that the comparative example has a significantly lower removal property than the thinner composition of the present invention.

In addition, the thinner compositions of the examples according to the present invention maintained equally excellent shape even when changing the rotational speed (rpm) condition of the EBR. This means that the thinner composition according to the present invention does not show an effect only in a specific condition, but exhibits the same performance in various conditions, and is more stable than a conventional thinner composition against changes in process conditions.

3. Coating uniformity ( Coating Uniformity ) evaluation

The thinner compositions of the examples and comparative examples were used to test the coating uniformity for the four photoresists and SOH and BARC in Table 2. According to the recipe shown in Table 7, after applying photoresist on an 8-inch silicon oxide substrate, a total of 16 points, 1-inch, 2-inch, 3-inch, 4-inch distances from the center of the wafer and the center of the wafer, in X shape, All 17 places (see FIG. 2) were measured to confirm that the photoresist was uniformly applied, and the results are shown in Table 8 below.

<Evaluation criteria>

◎: When the standard deviation of the applied film thickness is 1% or less

○: When the standard deviation of the applied film thickness is 2% or less

△: When the standard deviation of the applied film thickness is 3% or less

X: When the standard deviation of the applied film thickness is more than 3%

step Time(sec) Speed (rpm) Accelerator (rpm/sec) Dispensing (cc) One 5 0 10,000 2.0 (Thinner) 2 5 700 10,000 0 3 3 2,000 10,000 0 4 20 2,000 10,000 0.30 (PR) 5 5 700 10,000 0 6 5 0 10,000 0

division SOH(1.0cc) PR1(1.0cc) PR2(1.0cc) PR3(1.0cc) PR4(1.0cc) BARC(0.4cc) Example 1 ◎ ◎ ◎ ◎ ◎ ◎ Example 2 ◎ ◎ ◎ ◎ ◎ ◎ Example 3 ◎ ◎ ◎ ◎ ◎ ◎ Example 4 ◎ ◎ ○ ◎ ◎ ◎ Example 5 ◎ ○ ○ ○ ◎ ◎ Example 6 ◎ ○ ○ ○ ◎ ◎ Example 7 ◎ ◎ ◎ ◎ ◎ ◎ Example 8 ◎ ◎ ◎ ◎ ◎ ◎ Example 9 ◎ ◎ ◎ ◎ ◎ ◎ Example 10 ◎ ◎ ○ ◎ ◎ ◎ Example 11 ◎ ○ ○ ◎ ◎ ◎ Example 12 ◎ ○ ○ ◎ ◎ ◎ Example 13 ◎ ○ ○ ◎ ◎ ◎ Example 14 ○ ○ ○ ○ ○ ○ Example 15 ◎ ○ ○ ◎ ◎ ◎ Example 16 ○ ○ ○ ○ ◎ ○ Example 17 ○ △ △ ○ ○ ○ Comparative Example 1 X X X X X X Comparative Example 2 X X X X X X Comparative Example 3 X X X X X X Comparative Example 4 X X X X X X Comparative Example 5 △ X X X X △ Comparative Example 6 △ △ X △ △ △

4. rework Performance evaluation

Using the thinner compositions of the examples and comparative examples, the four photoresists in Table 2 and rework performance for SOH and BARC were tested. According to the recipe shown in Table 9, after applying 6 types of photoresist to the 8-inch silicon oxide substrate, the re-baking process was performed using each thinner composition for the wafer after the soft baking process. In the case of BARC, a rework process was performed using each thinner composition without heat treatment after application.

The surface state of the reworked silicon oxide substrate was evaluated using TOPCON's surface scan equipment (Model: WM-1500). The results are shown in Table 10 below.

<Evaluation criteria>

◎: When the number of surface particles of reworked silicon oxide surface particles is less than 1000 as a result of surface scan

○: When the number of surface particles that were reworked as a result of surface scan is 1000 or more and less than 2000

△: When the number of surface particles of reworked silicon oxide surface particles is 2000 or more and less than 3000 as a result of surface scan

X: When the number of surface particles of reworked silicon oxide surface particles is 3000 or more as a result of surface scan

step Time(sec) Speed (rpm) Accelerator (rpm/sec) Dispensing (cc) One 2 0 10,000 0 2 2 1000 10,000 0 3 4 1000 10,000 2.0 (Thinner) 4 9.5 4000 10,000 0 5 0 0 10,000 0

division SOH(1.0cc) PR1(1.0cc) PR2(1.0cc) PR3(1.0cc) PR4(1.0cc) BARC(0.4cc) Example 1 ◎ ◎ ◎ ◎ ◎ ◎ Example 2 ◎ ◎ ◎ ◎ ◎ ◎ Example 3 ◎ ◎ ◎ ◎ ◎ ◎ Example 4 ◎ ◎ ○ ◎ ◎ ◎ Example 5 ◎ ○ ○ ◎ ◎ ◎ Example 6 ◎ ○ ○ ◎ ◎ ◎ Example 7 ◎ ◎ ◎ ◎ ◎ ◎ Example 8 ◎ ◎ ◎ ◎ ◎ ◎ Example 9 ◎ ◎ ◎ ◎ ◎ ◎ Example 10 ◎ ◎ ○ ◎ ◎ ◎ Example 11 ◎ ○ ○ ◎ ◎ ◎ Example 12 ◎ ○ ○ ◎ ◎ ◎ Example 13 ◎ ○ ○ ◎ ◎ ◎ Example 14 ○ ○ ○ ○ ○ ◎ Example 15 ○ ◎ ○ ◎ ◎ ◎ Example 16 ○ ○ ○ ○ ○ ○ Example 17 ○ ○ △ ○ ○ ○ Comparative Example 1 X X X X X X Comparative Example 2 X X X X X X Comparative Example 3 X X X X X X Comparative Example 4 X X X X X X Comparative Example 5 △ X X X X △ Comparative Example 6 △ △ X △ △ △

Referring to Table 10, the thinner composition of the embodiment was found to have excellent rework performance because the number of reworked silicon oxide surface particles is less than 1000 or only 1000 to 2000.

On the other hand, in the thinner composition of the comparative example, the number of reworked silicon oxide surface particles exceeded 2000-3000 or 3000, and it was confirmed that the rework performance was deteriorated.

Claims (10)

Consists of at least one compound of propylene glycol alkyl (1 to 10 carbon atoms) ether acetate and alkyl (1 to 10 carbon atoms) alkoxy (1 to 10 carbon atoms) propionate and a ketone having 1 to 10 carbon atoms, the propylene glycol alkyl ether The content of at least one compound of acetate and the alkyl alkoxy propionate is 45% by weight or more of the total weight of the composition, a thinner composition for improving and removing resist coating properties.
The method according to claim 1, wherein the propylene glycol alkyl ether acetate is propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate and at least one member selected from the group consisting of propylene glycol butyl ether acetate, for improving the resist coatability and Thinner composition for removal.
The method according to claim 1, wherein the alkyl alkoxy propionate is methyl 3-methoxy propionate, methyl 3-ethoxy propionate, methyl 4-methoxy propionate, methyl 4-ethoxy propionate, ethyl 3 -At least one member selected from the group consisting of methoxy propionate, ethyl 3-ethoxy propionate, ethyl 4-methoxy propionate and ethyl 4-ethoxy propionate, for improving and removing resist coating properties Thinner composition.
The method according to claim 1, wherein the ketone is acetone, methyl ethyl ketone, methyl propyl ketone, methyl butyl ketone, methyl pentyl ketone, methyl hexyl ketone, methyl heptyl ketone, methyl octyl ketone, ethyl propyl ketone, ethyl butyl ketone and ethyl pentyl ketone A thinner composition for improving and removing resist coating properties, which is at least one selected from the group consisting of.
delete delete A method of treating a substrate comprising modifying a substrate with the thinner composition of claim 1 and applying SOH to the modified substrate.
The method of claim 7, wherein the SOH applied in the applying step is at least one of C-SOH and Si-SOH.
The method according to claim 7, further comprising the step of treating the substrate with the thinner composition after the SOH application step.
The method according to claim 9, further comprising the step of applying a photoresist after the thinner composition treatment of the SOH coated substrate, and then treating the thinner composition again.

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