KR20160072628A - Thinner composition for improving coating and removing performance of resist - Google Patents

Abstract

The present invention relates to a thinner composition for improving the coating and removing performance of a resist, and more specifically, to a thinner composition that contains compounds of Formula 1 and Formula 2 and thereby shows a high solubility with respect to various photoresists and bottom anti-reflective coatings (BARC), and furthermore shows high EBR capacity, can be used in the recovery process of wafers coated with photoresists, and significantly improves the capability for reducing resist consumption (RRC) and the coating performance of a photoresist. Also, the present invention relates to a method for treating wafers by using such thinner compositions.

Description

TECHNICAL FIELD [0001] The present invention relates to a thinner composition for improving and removing resist coating properties,

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

A photolithography process is a process of applying a photosensitive resin composition on a wafer during a process of manufacturing a semiconductor device, transferring a designed pattern, and then forming a fine circuit pattern such as a semiconductor integrated circuit through an etching process. This is accomplished by implementing a microcircuit pattern to be obtained through application, exposure, development, etching and stripping processes.

At this time, since the exposure process is implemented by a method of finely exposing a desired pattern to a coating film using light of a short wavelength ultraviolet ray region, it becomes sensitive to a contamination source. Thus, photoresist residues or contaminants applied to the substrate in the application process may be a source of contamination in the exposure process and need to be removed in advance, where thinner compositions have been used in edge bead removal (EBR) processes.

On the other hand, recently, photoresists using KrF and ArF (including ArF immersion) light sources having short wavelengths are applied, and thus the use amount of photoresist is increasingly influenced by the manufacturing cost of the integrated circuit. Therefore, there has been a demand to reduce the amount of photoresist used for cost reduction. For this purpose, the treatment composition is applied to the surface of the substrate before application of the photoresist so that the photoresist can be evenly applied over the entire surface of the substrate with only a small amount of photoresist A reducing resist consumption (RRC) process has been applied.

Japanese Laid-Open Patent No. 2001-188359 discloses an edge bead remover comprising propylene glycol ether acetate and methyl? -Hydroxy isobutyrate, which can be used in an EBR process and has excellent rework performance, but can be used in an RRC process There is no problem.

Japanese Patent Application Laid-Open No. 2005-2277770 also discloses that propylene glycol ether acetate and methyl 2-hydroxy-2-methylpropionate essentially contain ethyl lactate or ethyl 3-ethoxypropionate, Nonionic or ionic surfactants. However, when the surfactant is not included, it is difficult to apply to the RRC process. When the surfactant is included, the surfactant may be applied to the RRC process. However, there is a problem that the surfactant remains on the surface of the wafers and the rework performance is low.

,

Japanese Laid-Open Patent Publication No. 2001-188359 Japanese Patent Laid-Open No. 2005-2277770

It is an object of the present invention to provide a thinner composition having excellent solubility to various photoresists and a bottom anti-reflective coating (BARC).

It is an object of the present invention to provide a thinner composition which can be used simultaneously in an RBR process as well as an EBR process.

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

1. A thinner composition for improving and removing resist coating comprising a compound represented by the following formula (1) and a compound represented by the following formula (2)

[Chemical Formula 1]

(2)

.

.

2. The thinner composition for improving and removing resist properties according to 1 above, wherein the compound of Formula 1 and the compound of Formula 2 are contained in a weight ratio of 2: 8 to 8: 2.

3. The thinner composition for improving and removing resist coating according to 1 above, wherein the compound of Formula 1 and the compound of Formula 2 are contained in a weight ratio of 4: 6 to 6: 4.

4. The thinner composition according to 1 above, wherein the resist is a photoresist for i-line, KrF, ArF or EUV.

5. The thinner composition for improving and removing resist properties according to 1 above, which further comprises a surfactant.

6. The composition of claim 5 wherein said surfactant is selected from the group consisting of ethylene glycol methyl ether, ethylene glycol dimethyl ether, ethylene glycol ethyl ether, ethylene glycol methyl ethyl ether, ethylene glycol diethyl ether, diethylene glycol methyl ether, diethylene glycol dimethyl ether, Diethylene glycol dimethyl ether, diethylene glycol ethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, diethylene glycol propyl ether, diethylene glycol methyl propyl ether, diethylene glycol ethyl propyl ether and diethylene glycol dipropyl ether And at least one selected from the group consisting of the resin composition and the resin composition.

7. The method of treating a substrate with a thinner composition of any one of claims 1 to 6, prior to applying the photoresist to the substrate.

8. A method for processing a substrate, comprising applying a photoresist to a substrate and treating the substrate with a thinner composition of any one of claims 1 to 6 before the exposure to light.

The thinner composition for removing a resist of the present invention has excellent solubility in a variety of photoresists and a bottom antireflection film (BARC), and the EBR characteristics are remarkably high.

The resist thinner composition of the present invention exhibits excellent effects even in the RRC process.

The present invention relates to a thinner composition for improving and removing resist coating lines. More particularly, the present invention relates to a thinner composition for improving and removing resist coating lines, The present invention relates to a thinner composition for improving and removing resist which has high performance and which is applicable to a regeneration process of a wafer coated with a photoresist and which significantly improves RRC (reducing resist consumption) performance and coating ability of a photoresist, To a substrate processing method.

Hereinafter, the present invention will be described in detail.

The thinner composition for improving and removing resist properties of the present invention includes a compound represented by the following formula (1) and a compound represented by the following formula (2).

[Chemical Formula 1]

(2)

.

.

The compound represented by the formula (1) and the compound represented by the formula (2) all contain a substituent having a polarity in the molecule. When the compound having the above structure is used, the solubility of the lower antireflective coating (BARC) . Specifically, all terminal substituents connected to an ester group, a hydroxyl group, an alkoxy group, and the like, which exhibit intramolecular polarity, are all methyl groups. With the above-mentioned methyl group, the composition can maintain a polarity in an appropriate range for removing the bottom anti-reflective coating (BARC) In particular, in the case of formula (2), it is judged that the alkyl group connecting the terminal ester and the ether group plays a role of showing a polarity relative to the branched alkyl group because it is a non-branched chain alkyl group.

The mixing ratio of the compound represented by the formula (1) and the compound represented by the formula (2) is not particularly limited and may be, for example, in a weight ratio of 2: 8 to 8: 2, preferably 4: 6 to 6: By weight, more preferably in a weight ratio of 1: 1. In this case, it was judged that the polarity of the thinner composition was maintained in an appropriate range, the solubility in the resist was improved, the EBR characteristics were excellent, the proper volatilization rate was realized, and the RRC characteristics were also excellent.

The thinner composition for improving and removing resist properties according to the present invention may further comprise a surfactant in addition to the above components. When the composition further includes a surfactant, the composition may maintain an appropriate surface tension, The photoresist can be evenly applied to the entire surface of the substrate, which makes it easier to use in the RRC process.

Surfactants usable in the present invention include those known in the art without any particular limitation. Preferred examples of the solvent include ethylene glycol methyl ether, ethylene glycol dimethyl ether, ethylene glycol ethyl ether, ethylene glycol methyl ethyl ether, ethylene glycol diethyl ether, diethylene glycol methyl ether, diethylene glycol dimethyl ether, diethylene glycol ethyl ether, di Ethylene glycol dimethyl ether, ethylene glycol methyl ether, diethylene glycol diethyl ether, diethylene glycol propyl ether, diethylene glycol methyl propyl ether, diethylene glycol ethyl propyl ether, diethylene glycol dipropyl ether and triethylene glycol monomethyl ether. These may be used alone or in combination of two or more.

Further, the thinner composition for improving and removing resist properties according to the present invention may further include an additional solvent in addition to the above components, and the additional solvent may be any solvent that can be used in the art. Specific examples include methyl lactate, ethyl lactate, propylene glycol monomethyl ether propionate, propylene glycol monomethyl ether, propylene glycol methyl ether acetate (PGMEA), n-butyl acetate, ethyl ethoxypropionate, methyl methoxypropyl Phonate, 2-heptoneone, gamma butyrolactone, and the like can be used. These may be used alone or in combination of two or more.

The thinner composition according to the present invention has excellent solubility to various photoresist films and lower antireflective plate (BARC), has excellent EBR characteristics, can improve rework characteristics and coating performance of photoresist, It is also excellent. In particular, in the case of photoresists for i-line, KrF, ArF and EUV, since the basic structure of the photoresist to be constituted is different, it is necessary to control the compositional content of the organic solvent for improving solubility and coatability of them, The thinner composition of the present invention satisfies this.

The present invention provides a method of treating a substrate using the thinner composition according to the present invention.

The substrate processing method of the present invention includes the step of treating the substrate with the thinner composition and applying the photoresist to the substrate.

By applying the photoresist after treating the substrate with the thinner composition, the substrate can be coated with a small amount of photoresist, thereby improving the process cost and productivity.

Further, according to another embodiment of the substrate treating step of the present invention, the method further comprises the step of applying the photoresist and treating the substrate again with the thinner composition before the exposure step.

By treating the substrate with the thinner composition before the exposure step in this step, unnecessary photoresist applied to the edge portion or the rear portion of the substrate can be quickly and effectively removed.

Also in this process, the thinner composition can be treated before application of the photoresist. In this case, the amount of photoresist used can be reduced as described above, and the process cost and productivity can be improved.

The substrate processing method according to the present invention can be applied without any particular limitation as long as it is a product in which a photoresist is used, for example, an electronic device manufacturing method. For example, it can be applied to a semiconductor device or a manufacturing method of a thin film transistor liquid crystal display device.

It is to be understood that both the foregoing general description and the following detailed description of the present invention are exemplary and explanatory and are intended to be illustrative of the invention and are not intended to limit the scope of the claims. It will be apparent to those skilled in the art that such variations and modifications are within the scope of the appended claims.

Example  And Comparative Example

And the mixture was stirred at a speed of 500 rpm at room temperature for 1 hour to prepare a thinner composition.

division
(weight%) Formula 1 (2) solvent
(Ingredient / content) Surfactants
(Ingredient / content) Example 1 20 80 - - Example 2 30 70 - - Example 3 40 60 - - Example 4 50 50 - (TEGME / 1) Example 5 70 30 - (TEGME / 1) Example 6 80 20 - (TEGME / 1) Comparative Example 1 - - (A-1/100) - Comparative Example 2 - - (A-2/100) - Comparative Example 3 - - (A-3/100) (TEGME / 1) Comparative Example 4 - - (A-4/100) (TEGME / 1) Comparative Example 5 - - (A-1: A-2/50: 50) (TEGME / 1) Comparative Example 6 50 - (A-1/50) (TEGME / 1) Comparative Example 7 - 50 (A-1/50) (TEGME / 1)

화학식 2:

A-1:

A-2:

A-3:

A-4 :

계면활성제: 트리에틸렌글리콜모노메틸에테르(TEGME)(1)

(2)

A-1:

A-2:

A-3:

A-4:

Surfactant: triethylene glycol monomethyl ether (TEGME)

Experimental Example  One: Thinner  By composition EBR  ( edge bid removing Performance evaluation

After the photoresist shown in Table 2 was applied to an 8-inch silicon oxide substrate, the EBR experiment was conducted to remove the unnecessary photoresist film at the edge portions on the conditions shown in Table 3 for the thinner compositions of Examples and Comparative Examples . The thinner compositions of the examples and comparative examples were fed from a pressure vessel equipped with a pressure gauge at a pressure of 1 kgf and a flow rate of the thinner composition exiting the EBR nozzle was 10 to 30 cc / min. The removal performance of the unnecessary photoresist film was evaluated using an optical microscope, and the results are shown in Table 4 below.

<Evaluation Criteria>

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

○: Good linearity of EBR line uniformity of over 75% for EBR photoresist film

   condition

?: The shape of the edge portion after EBR is distorted due to the action of thinner dissolution

Χ: The tailing phenomenon occurred at the edge of the edge after EBR

 division  Composition type Resin series Film thickness (占 퐉)  PR 1  PR for i-line Novolac 1.10  PR 2 PR for KrF Acetal (PHS) 1.00  PR 3 PR for ArF Acrylate 0.18 BARC-1 BARC for KrF - 0.06 BARC-2 BARC for ArF - 0.04

division Rotational speed (rpm) Time (sec) Dispense condition 300-2000 7 Spin coating Adjusted according to the thickness of the photosensitive film - EBR condition 1 2000 20 EBR condition 2 2000 25 EBR condition 3 1300 6

division PR1 PR2 PR3 BARC-1 BARC-2 Example 1 ○ ○ ○ ○ ○ Example 2 ○ ○ ○ ○ ○ Example 3 ◎ ◎ ◎ ◎ ◎ Example 4 ◎ ◎ ◎ ◎ ◎ Example 5 ○ ○ ○ ○ ○ Example 6 ○ ○ ○ ○ ○ Comparative Example 1 △ △ △ △ △ Comparative Example 2 Χ Χ Χ Χ Χ Comparative Example 3 Χ Χ Χ Χ Χ Comparative Example 4 Χ Χ Χ Χ Χ Comparative Example 5 Χ Χ Χ Χ Χ Comparative Example 6 △ △ △ △ △ Comparative Example 7 △ △ △ △ △

As can be seen from Table 4, it was confirmed that the thinner composition of the present invention exhibits excellent EBR characteristics.

In the comparative examples having a structure similar to the formula (1) and the formula (2) according to the present invention, but having an ethyl group at the terminal or a linking group having a branched chain, the EBR characteristics are remarkably lowered compared to the examples.

Experimental Example  2: Photoresist  Depending on the type RRC  ( 감 resist consumption Performance evaluation

The RRC performance for the five photoresists and BARC of Table 2 was tested using the thinner compositions of the Examples and Comparative Examples. After applying 0.5 cc of thinner to an 8-inch silicon oxide substrate according to the recipe shown in Table 5, PR 1.2, 1.0 cc, PR 3: 0.8 cc, BARC-1: 0.5 cc and BARC-2: The coated state of the photoresist on the wafer after the application was evaluated, and the results are shown in Table 6.

<Evaluation Criteria>

&Amp; cir &amp;: When the photoresist is coated on the wafer by 98% or more

A: When the photoresist is coated on the wafer by 96% or more

?: When the photoresist is applied on the wafer by 94% or more

X: When the photoresist is applied on less than 94% of the wafer

step Time (sec) Speed (rpm) The accelerator (rpm / sec) Dispensing (cc) One 2.5 0 10000 0.5 (thinner) 2 1.5 900 10000 0 3 9.5 2000 10000 0 4 3.0 600 10000 0.4-1.2 (PR) 5 5.0 1500 10000 0 6 10.0 1000 10000 0

division PR1 PR2 PR3 BARC-1 BARC-2 Example 1 ○ ○ ○ ◎ ◎ Example 2 ◎ ◎ ◎ ◎ ◎ Example 3 ◎ ◎ ◎ ◎ ◎ Example 4 ◎ ◎ ◎ ◎ ◎ Example 5 ◎ ◎ ◎ ◎ ◎ Example 6 ○ ○ ○ ◎ ◎ Comparative Example 1 ○ ○ ○ ○ ○ Comparative Example 2 △ △ △ △ △ Comparative Example 3 △ △ △ △ △ Comparative Example 4 △ △ △ △ △ Comparative Example 5 △ △ △ △ △ Comparative Example 6 ○ ○ ○ ○ ○ Comparative Example 7 ○ ○ ○ ○ ○

As can be seen from Table 6, it was confirmed that the thinner composition of the present invention exhibits excellent RRC characteristics.

In comparison, in the comparative examples, since the polarity is somewhat lowered, it is confirmed that the RRC characteristics are lower than those of the embodiments.

Experimental Example  3: Photoresist  Evaluation of coating uniformity by type

The coating uniformity of the five photoresists and BARC of Table 2 was tested using the thinner compositions of the Examples and Comparative Examples. Photoresist was applied on an 8-inch silicon oxide substrate according to the recipe shown in Table 7, and then the film thickness of the photoresist was measured at 13 points in the center of the wafer and in the center of the wafer, And the standard deviation was calculated. The coating uniformity of the photoresist was evaluated by the calculated standard deviation, and the results are shown in Table 8.

<Evaluation Criteria>

?: When the standard deviation of the coating film thickness is 1% or less of the average film thickness

O: When the standard deviation of the coating film thickness is 2% or less of the average film thickness

?: When the standard deviation of the coating film thickness is 3% or less of the average film thickness

Χ: When the standard deviation of the coating film thickness exceeds 3% of the average film thickness

step Time (sec) Speed (rpm) The accelerator (rpm / sec) Dispensing (cc) One 2.5 0 10000 0.5 (thinner) 2 1.5 900 10000 0 3 9.5 2000 10000 0 4 3.0 600 10000 0.4-1.2 (PR) 5 5.0 1500 10000 0 6 10.0 1000 10000 0

division PR1 PR2 PR3 BARC-1 BARC-2 Example 1 ○ ○ ○ ◎ ◎ Example 2 ○ ○ ○ ◎ ◎ Example 3 ◎ ◎ ◎ ◎ ◎ Example 4 ◎ ◎ ◎ ◎ ◎ Example 5 ○ ○ ○ ◎ ◎ Example 6 ○ ○ ○ ◎ ◎ Comparative Example 1 △ △ △ ○ ○ Comparative Example 2 Χ Χ Χ ○ ○ Comparative Example 3 Χ Χ Χ ○ ○ Comparative Example 4 Χ Χ Χ ○ ○ Comparative Example 5 Χ Χ Χ ○ ○ Comparative Example 6 △ △ △ ○ ○ Comparative Example 7 △ △ △ ○ ○

As can be seen from Table 8, the thinner composition of the present invention was found to be uniform regardless of the type of the photoresist and the BARC, so that the coating performance of the photoresist was improved.

Experimental Example  4: Photoresist  Depending on the type rework  Performance evaluation

The rework performance of the five photoresists and BARC of Table 2 was tested using the thinner compositions of the Examples and Comparative Examples. Five photoresists were applied to an 8-inch silicon oxide substrate in accordance with the recipe shown in Table 9, and then the soft-baked wafer was reworked using each thinner composition. In the case of BARC, the rework process was performed using each thinner composition without heat treatment after application.

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

<Evaluation Criteria>

◎: Surface scan result shows that the number of surface particles of reworked oxide cone surface is less than 1000

○: Surface scan results show that the number of reworked oxide cone surface particles is more than 1000 and less than 2000

△: Surface scan result shows that the number of reworked oxide cone surface particles is more than 2000 and less than 3000

Χ: Surface scan results show that the number of reworked oxide cone surface particles is more than 3000

step Time (sec) Speed (rpm) The accelerator (rpm / sec) Dispensing (cc) One 2 0 10000 0 2 2 1000 10000 0 3 4 1000 10000 2.0 (Thinner) 4 9.5 4000 10000 0 5 0 0 10000 0

division PR1 PR2 PR3 BARC-1 BARC-2 Example 1 ◎ ◎ ◎ ◎ ◎ Example 2 ◎ ◎ ◎ ◎ ◎ Example 3 ◎ ◎ ◎ ◎ ◎ Example 4 ◎ ◎ ◎ ◎ ◎ Example 5 ◎ ◎ ◎ ◎ ◎ Example 6 ◎ ◎ ◎ ◎ ◎ Comparative Example 1 ○ ○ ○ ○ ○ Comparative Example 2 △ △ △ △ △ Comparative Example 3 △ △ △ △ △ Comparative Example 4 △ △ △ △ △ Comparative Example 5 △ △ △ △ △ Comparative Example 6 ○ ○ ○ ○ ○ Comparative Example 7 ○ ○ ○ ○ ○

As can be seen from Table 10, it was confirmed that the thinner composition of the present invention had excellent rework performance.

Claims (8)

A thinner composition for improving and removing resist coating comprising a compound represented by the following formula (1) and a compound represented by the following formula (2)
[Chemical Formula 1]

(2)

.
The thinner composition according to claim 1, wherein the compound of Formula 1 and the compound of Formula 2 are contained in a weight ratio of 2: 8 to 8: 2.
The thinner composition according to claim 1, wherein the compound of Formula 1 and the compound of Formula 2 are contained in a weight ratio of 4: 6 to 6: 4.
The thinner composition of claim 1, wherein the resist is a photoresist for i-line, KrF, ArF or EUV.
The thinner composition according to claim 1, further comprising a surfactant, for improving and removing resist applicability.
[6] The method of claim 5, wherein the surfactant is selected from the group consisting of ethylene glycol methyl ether, ethylene glycol dimethyl ether, ethylene glycol ethyl ether, ethylene glycol methyl ethyl ether, ethylene glycol diethyl ether, diethylene glycol methyl ether, diethylene glycol dimethyl ether, Diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol propyl ether, diethylene glycol methyl propyl ether, diethylene glycol ethyl propyl ether, and diethylene glycol dipropyl ether. At least one kind of a thinner composition for improving and removing resist applicability.
7. A method of processing a substrate with a thinner composition according to any one of claims 1 to 6 before applying the photoresist to the substrate.
A method for processing a substrate, comprising the steps of: applying a photoresist to a substrate, and then treating the substrate with the thinner composition of any one of claims 1 to 6 before exposure to light.