KR20160071307A - Cleansing composition for removal of photoresist post-ashing residue - Google Patents

Abstract

The present invention relates to a detergent composition for a metal film and, more specifically, to a detergent composition for removing residues, impurities, contaminants, and the like remaining on the top of a metal substrate after ashing, regarding a semiconductor manufacturing process. The detergent composition comprises (A) alkylammonium fluoride, (B) an organic sulfonic acid-based compound, and (C) a polar, protogenic, and organic solvent.

Description

CLEANSING COMPOSITION FOR REMOVAL OF PHOTORESIST POST-ASHING RESIDUE BACKGROUND OF THE INVENTION [0001]

The present invention relates to a detergent composition for a metal film, and more particularly to a detergent composition for a metal film which removes residues, contaminants and residues remaining on a metal substrate after ashing in a semiconductor manufacturing process.

Semiconductor devices (semiconductor devices) are manufactured through lithography, film formation, exposure, etching, and ashing processes. It is required to remove the resist, organic matter, fine particles of an inorganic substance, metal impurity, and the like on the surface of the substrate and clean it before proceeding to the next step after completion of each step.

In particular, after the end of the etching step, the final masking process can be performed only if the resist mask is removed from the protective region of the wafer, which is performed using a suitable plasma ashing gas or a wetting chemical stripper in the plasma ashing step . Removal and neutralization of residues remaining after such etching / ashing processes are important in terms of eliminating undesirable materials that cause inhalation of moisture and corrosion of the metal structure. When the following process steps are carried out with such contaminants and residues adhering, the pinholes and pits of the film, corrosion of the substrate, disconnection of the circuit wiring, bridge, and electric resistance are unnecessarily increased, do.

Therefore, cleaning for removing residual contaminants is carried out between the respective processes, and a lot of research has been conducted on the cleaning agent for this.

Conventional detergent compositions for semiconductors and TFT-LCDs have insufficient ability to remove oil, inorganic contaminants and particles, and when polyhydroxybenzene chelate compounds such as catechol or gallic acid are used, precipitation problems may occur during prolonged use. In addition, the conventional detergent composition including a carboxylic acid and the like has a disadvantage in that it is not excellent in corrosion resistance against the film quality of germanium (Ge), silicon germanium (SiGe), and the like and has excessive erosion resistance.

SUMMARY OF THE INVENTION The present invention has been made in order to solve the problems of the prior art,

It is an object of the present invention to provide a detergent composition for a semiconductor substrate which is effective in removing residual polymer residues, photoresist, organic residues and residues after plasma ashing after the ashing process and has a low etching rate for a metal substrate do.

According to the present invention,

(A) an alkylammonium fluoride, (B) an organic sulfonic acid compound, and (C) a polar protic organic solvent.

The detergent composition of the present invention contains an alkylammonium fluoride, an organic sulfonic acid compound, and a polar protic organic solvent, so that the cleaner composition of the present invention has high cleaning property against residue after an ashing process in a semiconductor manufacturing process, ) Can provide a low effect.

Hereinafter, the present invention will be described in more detail.

According to the present invention,

Metals such as metal films that may be exposed to the cleaning composition in the semiconductor manufacturing process may be removed from the substrate without any undesirable degradation and the polymer residue, photoresist residue, organic residues, residue after plasma ashing, Which can remove residues, such as residues, or other non-limiting residues and contaminants.

That is, the present invention relates to a detergent composition for a metal film which removes residues and impurities remaining on a metal substrate after a process such as photoresist ashing after ion implantation in a semiconductor manufacturing process,

(A) an alkylammonium fluoride, (B) an organic sulfonic acid compound, and (C) a polar protic organic solvent.

Further, the detergent composition of the present invention may further comprise at least one member selected from a polyhydric alcohol and a silicon-based compound.

The detergent composition of the present invention can provide the effect of easily removing residues and impurities such as resist, organic insulating film and transparent resin as well as minimizing damage to the metal film during cleaning by the above-mentioned composition.

The metal film may be made of, for example, a Ge alloy such as germanium (Ge) or silicon germanium (SiGe), a silicon oxide (SiOx), a copper (Cu), a copper alloy, (TiN), titanium nitride (TiN), tantalum (Ta), tantalum nitride (TaN), tungsten (W), titanium / tungsten Arsenide (GaAs) or a metal film for a semiconductor substrate which is not limited to this, and the detergent composition of the present invention is compatible with this. That is, the detergent composition of the present invention does not cause damage to the membrane in the process of removing impurities on the membrane quality described above.

Hereinafter, each component will be described in detail.

(A) Alkylammonium Fluoride

The alkyl ammonium fluoride (A) included in the detergent composition of the present invention serves to provide a fluoride ion (F < ^- >) for removing residues after ashing.

The alkylammonium fluoride is not particularly limited, but specific examples thereof include tetramethylammonium fluoride, tetraethylammonium fluoride, tetrapropylammonium fluoride and tetrabutylammonium fluoride, and they may be used singly or in combination of two or more Can be mixed and used.

The amount of the alkylammonium fluoride is preferably 2 to 10% by weight, more preferably 2 to 8% by weight based on the total weight of the detergent composition. If the alkylammonium fluoride is contained in an amount of less than 2% by weight, the residue cleaning rate after ashing is decreased. If it exceeds 10% by weight, damage to the metal film such as silicon oxide (SiOx) may occur.

(B) an organic sulfonic acid compound

The sulfonic acid-based compound contained in the detergent composition of the present invention is a main component for removing residues after ashing. Specific examples thereof include methanesulfonic acid, ethanesulfonic acid, 1-propanesulfonic acid, para-toluenesulfonic acid, But the present invention is not limited thereto, and they may be used alone or in combination of two or more.

The organic sulfonic acid compound contained in the detergent composition of the present invention is excellent in the effect of inhibiting corrosion by forming a film on a metal film as compared with other organic acids such as carboxylic acid compounds such as formic acid and acetic acid. ) Can be minimized.

The organic sulfonic acid compound is preferably contained in an amount of 2 to 10% by weight, more preferably 2 to 8% by weight based on the total weight of the detergent composition. If the organic sulfonic acid compound is contained in an amount of less than 2% by weight, the cleaning rate is decreased. If the organic sulfonic acid compound is more than 10% by weight, it may cause defects in the underlying film.

(C) Polarity Quantum property  Organic solvent

The polar protic organic solvent of the present invention is included in the detergent composition to dissolve the alkylammonium fluoride and the organic sulfonic acid compound described above and exhibits the activity of the alkylammonium fluoride due to its polar nature It is advantageous to heighten.

The polar, quantum organic solvent of the present invention is not particularly limited as long as it is a polar, quantum organic solvent capable of dissolving the alkylammonium fluoride (A) and the organic sulfonic acid compound (B), and specific examples thereof include alkyl alcohols, .

Specific examples of the alkyl alcohols include methanol, ethanol, propanol, isopropanol, butanol, isobutanol, t-butanol, pentanol, hexanol, heptanol and octanol, , Propanol and butanol may be used,

Specific examples of the glycols include alkylene glycols such as ethylene glycol, propylene glycol and butylene glycol; Ethylene glycol monomethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol Monoethyl ether, monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monoisopropyl ether, triethylene glycol monobutyl ether, polyethylene glycol monomethyl ether, polyethylene glycol monobutyl ether, propylene glycol monomethyl ether , Dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, and other alkylene glycol monoalkyl ethers; Propylene glycol monomethyl ether acetate, tetrahydroperfuryl alcohol, and the like, but it is not limited thereto, and it is more preferably selected from ethylene glycol, propylene glycol, butylene glycol, ethylene glycol monomethyl ether and ethylene glycol monoethyl ether May be used.

These may be used alone or in combination of two or more.

The polar protic organic solvent is preferably contained in an amount of 75 to 95% by weight, and more preferably 80 to 95% by weight based on the total weight of the detergent composition. If the amount of the polar protic organic solvent is less than 75% by weight, damage to the metal film may be caused. If the amount exceeds 95% by weight, the cleaning effect of the cleaning composition may decrease.

(D) a polyhydric alcohol

The detergent composition of the present invention may further include a polyhydric alcohol in addition to the above-mentioned components. The polyhydric alcohol is a compound having three or more hydroxyl groups (-OH), and serves to minimize the damage of the underlying film when removing residues after ashing. The lower film may be, but not limited to, silicon oxide (SiOx), germanium (Ge), or silicon germanium (SiGe).

Specific examples of the polyhydric alcohol include glycerine, erythritol, threitol, xylitol, arabitol, sorbitol and mannitol, and the like. But the present invention is not limited thereto, and one or more species selected therefrom may be used together.

The polyhydric alcohol is preferably contained in an amount of 1 to 5% by weight, more preferably 2 to 5% by weight based on the total weight of the detergent composition. When polyhydric alcohols are contained within the above range, the protective effect against the lower film quality is excellent and the corrosion prevention against the silicon oxide film is excellent.

(E) Silicon-based compound

The detergent composition of the present invention may further contain a silicon-based compound in addition to the above-mentioned components. The silicon-based compound (E) provides an effect of minimizing the damage of the underlying film upon removal of residues after ashing. The film quality may be, but not limited to, silicon oxide (SiOx), germanium (Ge), and silicon germanium (SiGe).

Specific examples of the silicon-based compound include aminoalkylalkoxysilane-based compounds such as 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, aminobutyltrimethoxysilane and aminobutyltriethoxysilane; Aminophenyl trimethoxysilane, para-aminophenyl trimethoxysilane, 3-aminopropyl silanetriol, methyl triethoxysilane, triethoxy (ethyl) silane, tri (Octyl) silane, triethoxy (1-phenylethenyl) silane, triethoxy [4- (trifluoromethyl) phenyl] silane, triethoxy (Methyl) silane, triphenyl (vinyl) silane, trimethoxy (propyl) silane, trimethoxy (octadecyl) silane, triethoxysilane, tetrakis But are not limited to, silane, trimethyl (phenyl) silane, trimethyl (vinyl) silane, trimethoxy (2-phenylethyl) silane, trimethyl (phenoxy) silane, One or two or more species selected therefrom may be used together. Among them, from the viewpoint of enhancing the corrosion inhibiting effect on the protective film, it is preferable to use 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, meta-aminophenyltrimethoxysilane, Silane, 3-aminopropyl silanetriol, and methyl triethoxy silane may be preferably used.

The amount of the silicon-based compound is preferably 0.1 to 2% by weight, more preferably 1 to 2% by weight based on the total weight of the detergent composition. When the silicon-based compound is contained in an amount of less than 0.1% by weight, the effect on the film quality may be insignificant, and if it exceeds 2% by weight, the cleaning speed may decrease.

Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples. However, the following examples are intended to further illustrate the present invention, and the scope of the present invention is not limited by the following examples. The following examples can be appropriately modified and changed by those skilled in the art within the scope of the present invention.

Example  And Comparative Example : Preparation of detergent composition

The cleaning agent compositions of Examples 1 to 20 and Comparative Examples 1 to 10 were prepared by mixing the components shown in the following Table 1 according to the determined composition ratios.

division
(weight%) Alkylammonium
Fluoride ammonium
Fluoride Organic acid Organic solvent Close
Alcohol Silicon-based
compound D
I
W ingredient content ingredient content ingredient content ingredient content ingredient content ingredient content Example 1 A-1 4 - - B-1 5 C-1 91 - Example 2 A-1 4 - - B-1 5 C-2 91 - Example 3 A-1 4 - - B-1 5 C-1 86 D-1 5 - Example 4 A-1 2 - - B-1 5 C-1 93 - Example 5 A-1 10 - - B-1 5 C-1 85 - Example 6 A-1 4 - - B-1 10 C-1 86 - Example 7 A-2 4 - - B-1 5 C-1 91 - Example 8 A-1 4 - - B-2 5 C-1 86 D-1 5 - Example 9 A-1 4 - - B-1 5 C-2 86 D-1 5 - Example 10 A-1 2 - - B-1 5 C-1 92 D-1 One - Example 11 A-1 4 - - B-1 5 C-1 86 D-2 5 - Example 12 A-1 4 - - B-1 5 C-1 89 E-1 2 Example 13 A-1 2 - - B-1 5 C-1 91 E-1 2 Example 14 A-1 10 - - B-1 5 C-1 83 E-1 2 Example 15 A-1 4 - - B-1 10 C-1 84 E-1 2 Example 16 A-2 4 - - B-1 5 C-1 89 E-1 2 Example 17 A-1 4 - - B-2 5 C-1 89 E-1 2 Example 18 A-1 4 - - B-1 5 C-2 89 E-1 2 Example 19 A-1 2 - - B-1 5 C-2 92.9 E-1 0.1 Example 20 A-1 4 - - B-1 5 C-1 89 E-2 2 Comparative Example 1 - - F-1 4 B-1 5 C-1 86 D-1 5 - Comparative Example 2 - - F-2 4 B-1 5 C-1 86 D-1 5 - Comparative Example 3 - - F-1 4 B-1 5 C-1 66 D-1 5 20 Comparative Example 4 A-1 4 - - G-1 5 C-1 86 D-1 5 - Comparative Example 5 A-1 4 - - G-2 5 C-1 86 D-1 5 - Comparative Example 6 - - F-1 4 B-1 5 C-1 89 E-1 2 Comparative Example 7 - - F-2 4 B-1 5 C-1 89 E-1 2 Comparative Example 8 - - F-1 4 B-1 5 C-1 69 E-1 2 20 Comparative Example 9 A-1 4 - - G-1 5 C-1 89 E-1 2 Comparative Example 10 A-1 4 - - G-2 5 C-1 89 E-1 2 A-1: tetrabutylammonium fluoride
A-2: Tetramethylammonium fluoride
B-1: Methanesulfonic acid
B-2: Para-toluenesulfonic acid
C-1: Ethylene glycol
C-2: methanol
D-1: glycerin
D-2: Sorbitol
E-1: 3-aminopropyltriethoxysilane
E-2: Meta-aminophenyl trimethoxysilane
F-1: Ammonium fluoride
F-2: Ammonium bifluoride
G-1: Formic acid
G-2: Acetic acid

< Experimental Example >

Experimental Example  One.

One) Ashing  Removal of post-mortem and evaluation of damage to underlying membrane

Photoresist was coated on a silicon wafer on which germanium (Ge) was deposited. After patterning through exposure and development, ion implantation was performed, and an ashing process was performed to prepare a substrate. A specimen having a size of 2 x 2 cm was prepared. Each of the compositions of Examples 1 to 20 and Comparative Examples 1 to 10 in Table 1 was prepared and heated to 60 DEG C, and the substrate was immersed for 2 minutes and 10 minutes and then washed with water. The results are shown in Table 2. The results are shown in Table 2 below. The results are shown in Table 2 below. The results are shown in Table 2 below. Respectively.

&Lt; Evaluation Criteria for Residue Removal After Ashing >

◎: 95% or more removed

○: 90% to less than 95% removed

?: Less than 80% to less than 90% removed

X: Less than 80% removed

2) Solubility

The solubility and the occurrence of precipitation of the compositions of Examples 1 to 20 and Comparative Examples 1 to 10 were visually observed and shown in Table 2.

<Evaluation Criteria for Solubility>

○: No under-precipitation occurs and transparency

X: Under-precipitation and suspension of solution occur

Experimental Example  2.

A silicon wafer on which silicon germanium (SiGe) was deposited was used in the same manner as in Experimental Example 1, and the results are shown in Table 2.

Experimental Example  3.

A silicon wafer on which silicon oxide (SiO ₂ ) was deposited was used in the same manner as in Experimental Example 1, and the results are shown in Table 2.

division After ashing
Remove residues Ge etch rate
(Å / min) SiGe etch rate
(Å / min) SiOx etch rate
(Å / min) Solubility Example 1 ◎ <1 <1 3.2 ○ Example 2 ◎ <1 <1 4.2 ○ Example 3 ◎ <1 <1 <1 ○ Example 4 ○ <1 <1 <1 ○ Example 5 ◎ 3.2 3.6 4.8 ○ Example 6 ◎ 2.9 3.0 3.9 ○ Example 7 ◎ <1 <1 3.6 ○ Example 8 ◎ <1 <1 <1 ○ Example 9 ◎ <1 <1 1.2 ○ Example 10 ○ <1 <1 1.6 ○ Example 11 ◎ <1 <1 <1 ○ Example 12 ◎ <1 <1 <1 ○ Example 13 ○ <1 <1 <1 ○ Example 14 ◎ 3.5 3.8 5.0 ○ Example 15 ◎ 3.0 3.2 4.2 ○ Example 16 ◎ <1 <1 <1 ○ Example 17 ◎ <1 <1 <1 ○ Example 18 ◎ <1 <1 1.0 ○ Example 19 ○ <1 <1 1.8 ○ Example 20 ◎ <1 <1 <1 ○ Comparative Example 1 - - - - X Comparative Example 2 - - - - X Comparative Example 3 ◎ 6.7 7.2 10.8 ○ Comparative Example 4 ◎ 21.5 23.5 19.4 ○ Comparative Example 5 ◎ 19.0 20.1 16.2 ○ Comparative Example 6 - - - - X Comparative Example 7 - - - - X Comparative Example 8 ◎ 7.6 8.2 12.6 ○ Comparative Example 9 ◎ 22.3 25.1 23.5 ○ Comparative Example 10 ◎ 19.4 21.2 20.5 ○

As shown in Table 2, the detergent compositions of Examples 1 to 20 exhibit excellent residue removability after ashing, and are less susceptible to damage to the metal film, resulting in remarkably low damage to the Ge, SiGe, and SiO ₂ films . On the other hand, in the case of Comparative Examples 1 to 10, the residue removal property was not excellent or the attack to membrane quality was large. In Comparative Examples 1, 2, 6 and 7, As shown in Fig. Further, it was confirmed that when water was added to the cleaning agent composition to prevent the occurrence of precipitation (Comparative Examples 3 and 8), damage to the lower film occurred and it was not preferable.

Claims (12)

(A) an alkylammonium fluoride, (B) an organic sulfonic acid compound, and (C) a polar protic organic solvent. The method according to claim 1,
Polyhydric alcohols, and silicon-containing compounds. &Lt; RTI ID = 0.0 &gt; 11. &lt; / RTI &gt; The method according to claim 1,
With respect to the total weight of the detergent composition,
(A) 2 to 10% by weight of alkylammonium fluoride,
(B) 2 to 10% by weight of an organic sulfonic acid-based compound, and
(C) from 75 to 95% by weight of a polar, quantum organic solvent. The method according to claim 1,
Wherein the alkylammonium fluoride is at least one selected from tetramethylammonium fluoride, tetraethylammonium fluoride, tetrapropylammonium fluoride, and tetrabutylammonium fluoride. The method according to claim 1,
Wherein the organic sulfonic acid compound is at least one selected from methanesulfonic acid, ethanesulfonic acid, 1-propanesulfonic acid, para-toluenesulfonic acid and benzenesulfonic acid. The method according to claim 1,
Wherein the polar protic organic solvent is at least one selected from alkyl alcohols and glycols. The method of claim 2,
With respect to the total weight of the detergent composition,
1 to 5% by weight of polyhydric alcohol, and
And 0.1 to 2% by weight of a silicon-containing compound. The method of claim 2,
The polyhydric alcohol is at least one selected from glycerine, erythritol, threitol, xylitol, arabitol, sorbitol and mannitol. &Lt; / RTI &gt; The method of claim 2,
The silicon-based compound is preferably selected from the group consisting of 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, meta-aminophenyltrimethoxysilane, meta-aminophenyltriethoxysilane, Triethoxysilane, and triethoxysilane. The method of claim 6,
The alkyl alcohols are at least one selected from methanol, ethanol, propanol and butanol,
Wherein the glycols are at least one selected from ethylene glycol, propylene glycol, butylene glycol, ethylene glycol monomethyl ether, and ethylene glycol monoethyl ether. The method according to claim 1,
Wherein the detergent composition is used for cleaning a metal film after ashing in a semiconductor manufacturing process. The method of claim 11,
The metal film may be formed of a metal such as germanium (Ge), a Ge alloy, silicon oxide, copper (Cu), a copper alloy, aluminum (Al), an aluminum alloy, titanium (Ti) (TiN), tantalum (Ta), tantalum nitride (TaN), tungsten (W), titanium tungsten (TiW), silicon nitride (SiN) or gallium arsenide (GaAs).