KR20210036690A - Cleaning solution composition of semiconductor or display substrate - Google Patents

Abstract

The present invention relates to a cleaning composition for a semiconductor or display substrate, by containing: an alkali compound; organic solvents containing glycerol; and water, which has excellent removal power of inorganic particles (especially Ag) generated in an etching step, prevents the inorganic particles from re-adhering to the substrate, prevents corrosion of metal films (eg, Al, Ti, Ag, ITO, etc.), and prevents damage to an organic film by preventing the composition from penetrating into the organic film (for example, a photoresist film) to have excellent stability over time of the composition itself.

Description

Cleaning agent composition for semiconductor or display substrate {CLEANING SOLUTION COMPOSITION OF SEMICONDUCTOR OR DISPLAY SUBSTRATE}

The present invention relates to a cleaning agent composition for a semiconductor or display substrate.

A semiconductor or display device such as a charge-coupled device (CCD) and a memory is manufactured by forming a fine electronic circuit pattern on a substrate using a photolithography technique. Specifically, the semiconductor device is a metal film or metal wiring (Cu, Co, Ag, Mg, IZO/Ag/IZO, ITO/AG/ITO, MO/Ag/ITO, etc.), which becomes a wiring material formed on a substrate, and an etching stop film. And a photoresist film formed on a laminated film having an interlayer insulating film, etc., manufactured through a photolithography process and a dry etching process (e.g., plasma etching treatment), and a dry or wet etching process for peeling the resist film if necessary. It is manufactured through.

Conventionally, in order to realize a pattern miniaturization, the use of a metal material-based resist film (also referred to as a metal hard mask) such as TiX and AlOx as a resist film is increasing. In this way, when a metal hard mask is used as a resist film, an etching process is usually performed using a metal hard mask as a mask, and a hole based on the pattern shape of the metal hard mask is formed to expose the metal film or the metal wiring surface as a wiring film. The process of making is performed.

At this time, in the substrate that has undergone the etching process, residues such as etching residues are adhered on the metal film or metal wiring and/or on the interlayer insulating film, and a cleaning operation for treating them is required.

In this regard, Korean Patent Application Publication No. 10-2015-0000129 discloses inorganic dyes 0.1-20% by weight, surfactant 0.1-15% by weight, amines 0.1-20% by weight, amide 0.1-40% by weight, alcohols 0.1- Description of the glass cleaner composition for removing impurities such as oil and particles that may exist on the glass surface by adjusting the total weight to 100% by weight by adding 15% by weight, 0.1-5% by weight of an antifoaming agent, and the remaining amount of ultrapure water However, the cleaning agent composition has a problem in that the metal substrate, particularly the Al substrate, is corroded and penetrates the lower organic film (photoresist film) to damage the lower organic film.

Republic of Korea Patent Publication No. 10-2015-0000129 (2015.01.02.)

The present invention has been made to solve the above problems, and an object thereof is to provide a cleaning agent composition for a semiconductor or display substrate capable of removing inorganic particles without corrosion of a metal film or metal wiring or invasion of an organic film.

The cleaning agent composition for a semiconductor or display substrate of the present invention for achieving the above object is an alkali compound; An organic solvent containing glycerol; And water;

The cleaning agent composition for a semiconductor or display substrate of the present invention has excellent removal power of inorganic particles generated after etching, prevents the inorganic particles from being reattached, has excellent aging stability, and has an effect of preventing corrosion on metal films or metal wirings. It is excellent and does not infringe on the organic film, so it has the advantage of preventing damage to the organic film.

In the present invention, when a part "includes" a certain component, it means that other components may be further included rather than excluding other components unless otherwise stated.

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

The cleaning agent composition for a semiconductor or display substrate according to an aspect of the present invention includes an alkali compound; Corrosion inhibitors including glycerol; And water; by including, it has excellent removal power of inorganic particles (especially Ag) generated in the etching step, prevents the inorganic particles from being reattached to the substrate, and prevents re-adhesion of the inorganic particles to the substrate, Ti, Ag, ITO, etc.), and by preventing the composition from penetrating into the organic film (e.g., photoresist film), the organic film is prevented from being damaged, and the composition itself has excellent stability over time. have.

Alkali compound

The cleaning agent composition for a semiconductor or display substrate according to an aspect of the present invention contains an alkali compound.

The alkali compound serves to remove metallized inorganic particles remaining after wet or dry etching or inorganic particles introduced from the outside.

The kind of alkali compound used in the art may be used without particular limitation, and examples thereof include inorganic alkali compounds such as potassium hydroxide and sodium hydroxide; Quaternary ammonium hydrates such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tris(2-hydroxyethyl)methylammonium hydroxide, ethyltrimethylammonium hydroxide, and choline hydroxide, and the like. , These may be used alone or in combination of two or more.

According to an embodiment of the present invention, the alkali compound is contained in an amount of 0.05 to 10% by weight, preferably 0.1 to 5% by weight, and more preferably 0.1 to 3% by weight, based on 100% by weight of the total composition containing the same. I can. When the alkali compound satisfies the above range, the removal power of inorganic particles or the corrosion prevention power of the metal film or metal wiring may be more improved, and when the alkali compound is contained within the above range, the removal power of the inorganic particles may be slightly lowered. In the case of exceeding the above range, the effect of increasing the removal power of inorganic particles according to the increase in the content may be insufficient, and it may be somewhat difficult to secure the corrosion preventing power of the metal film or the metal wiring.

Organic solvent

The cleaning agent composition for a semiconductor or display substrate according to an aspect of the present invention includes an organic solvent containing glycerol. As described above, by including glycerol as an organic solvent, the composition of the present invention prevents inorganic particles from re-adhering to the substrate, and prevents the composition from penetrating into the organic film, thereby preventing damage to the organic film, and There is an advantage in that the corrosion-preventing effect of metal wiring is excellent, and in particular, the composition itself is excellent in aging stability, so that even when the composition is used for a long time, the removal power of inorganic particles is excellently maintained.

The glycerol may be included in an amount of 1 to 50% by weight, preferably 3 to 40% by weight, and more preferably 3 to 30% by weight, based on 100% by weight of the total composition comprising the same. When the glycerol is included within the above range, the aging stability of the composition itself may be more improved, the corrosion prevention power for the metal film or metal wiring may be more improved, and the removal power of inorganic particles may be further improved. If the glycerol is contained in less than the above range, the stability over time or the corrosion protection of the metal film or metal wiring may be slightly lowered, and if it exceeds the above range, the corrosion protection of the metal wiring or the re-adsorption of inorganic particles according to the increase of the component may be prevented. The effect of improving power is insufficient, so economic feasibility may be poor.

According to an embodiment of the present invention, the cleaning agent composition for a semiconductor or display substrate may further contain an organic solvent other than glycerol.

The organic solvent that may be further included is not particularly limited, but, for example, 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 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 propylene glycol monomethyl ether acetate, and the like, each of which alone or Two or more types can be mixed and used.

water

The cleaning agent composition for a semiconductor or display substrate according to an aspect of the present invention contains water.

The water may preferably be deionized water, and the content of the water may be included as the remaining amount of the content of each component included in the above-described detergent composition with respect to 100% by weight of the total composition.

Corrosion inhibitor

According to an embodiment of the present invention, the detergent composition of the present invention may further include a corrosion inhibitor.

The corrosion inhibitor may be, for example, monocarboxylic acids such as formic acid, acetic acid, and propionic acid; Dicarboxylic acids such as hydroxyl acid, malonic acid, succinic acid, glutanoic acid, adipic acid, pimelic acid, maleic acid, furmaic acid, and glutaconic acid; Organic acids such as tricarboxylic acids such as trimellitic acid and tricarboxylic acid, hydroxyacetic acid, lactic acid, salicylic acid, malic acid, tartaric acid, citric acid, gluconic acid, silsesquioxane, and oxycarboxylic acid; Succinic amide ester, maleic amide ester, maleic amide ester, fumaric amide ester, oxalic amide ester, malonic amide ester, glutaric amide ester, acetic amide ester, lactic amide ester, citric amide ester, tar Organic acid amide ethers such as taric amide ester, glucolic amide ester, formic amide ester, and uric amide ester; Benzotriazole, tolitrizol, methyl tolitrizol, 2,2'-[[[benzotriazole]methyl]imino]bisethanol, 2,2'-[[[methyl-1 hydrogen-benzotria Zol-1-yl]methyl]imino]bismethanol, 2,2'-[[[ethyl-1hydrogen-benzotriazol-1-yl]methyl]imino]bisethanol, 2,2'-[[ [Methyl-1H-benzotriazol-1-yl]methyl]imino]bisethanol, 2,2'-[[[methyl-1H-benzotriazol-1-yl]methyl]imino]biscarboxylic acid, 2 ,2'-[[[methyl-1H-benzotriazol-1-yl]methyl]imino]bismethylamine and 2,2'-[[[amine-1H-benzotriazol-1-yl]methyl] Imino]bisethanol 4-methyl-1H-benzotriazole, 6-methyl-4,5,6,7-tetrahydro-1H-benzo[1,2,3]triazole, 5,6-dimethyl-4 ,5,6,7-tetrahydro-1H-benzo[1,2,3]triazole, 4,6-dimethyl-4,5,6,7-tetrahydro-1H-benzo[1,2,3] Azole compounds such as triazole and 5-methyl-1H-benzotriazole; 2,6-dimethylphenol, 2,4,6-trimethylphenol, 2,6-diethylphenol, 2,6-diethyl-4-methylphenol, 2,6-dipropylphenol, 2,6-tripro Symmetrical phenolic compounds such as -4-methylphenol, 2,6-di-t-butylphenol, 2,4,6-tri-t-butylphenol, and 2,6-di-t-butyl-4-methylphenol ; Gallate compounds such as pyrogallol, methyl gallate, propyl gallate, dodecyl gallate, octyl gallate, and gallic acid; Polyhydric alcohol compounds such as sorbitol, xylitol, mannitol, and maltitol; And the like, but are not limited thereto, and these may be used alone or in combination of two or more.

As described above, when the detergent composition of the present invention further contains a corrosion inhibitor other than glycerol, the content is 0 to 5% by weight, preferably 0.001 to 3% by weight, based on 100% by weight of the total composition further comprising the corrosion inhibitor. %, more preferably 0.01 to 3% by weight may be included. When a corrosion inhibitor other than glycerol is included within the above range, corrosion prevention power for a metal film or a metal wiring may be further improved.

According to an embodiment of the present invention, the electrical conductivity of the composition for a semiconductor or display substrate may be 2 to 10 mS/cm, preferably 3 to 9 mS/cm, more preferably 3 to 8 mS/cm. When the electrical conductivity of the cleaning composition satisfies the above range, the removal power of inorganic particles generated after etching is more improved, the re-adsorption of the inorganic particles to the substrate can be more effectively prevented, and the metal film or metal wiring is corroded. The effect of preventing the phenomena from becoming a problem may be improved.

Hereinafter, preferred embodiments are presented to aid in the understanding of the present invention, but the following examples are only illustrative of the present invention, and that various changes and modifications are possible within the scope of the present invention and the scope of the technical idea are obvious to those skilled in the art. , It is natural that such modifications and modifications fall within the scope of the appended claims. In the following Examples and Comparative Examples, "%" and "parts" indicating the content are based on weight unless otherwise specified.

Example And Comparative example

A detergent composition was prepared with each composition and content shown in Table 1 below.

(Unit: wt%) Alkali compound Organic solvent Corrosion inhibitor Deionized water Electrical conductivity Kinds content Kinds content Kinds content content (mS/cm) Example 1 TMAH 0.5 Glycerol 19.5 - - 80.0 6.14 Example 2 TEAH 1.0 Glycerol 19.0 - - 80.0 9.01 Example 3 KOH 0.1 Glycerol 14.9 - - 85.0 3.25 Example 4 TMAH 0.4 Glycerol 10.0 A 0.1 89.5 4.88 Example 5 TMAH 0.3 Glycerol 4.2 B 0.5 95.0 4.52 Example 6 TMAH 0.5 Glycerol 7.45 C 0.05 92.0 6.87 Example 7 KOH 0.1 Glycerol 30 - - 69.9 2.45 Example 8 TMAH 3 Glycerol 25 - - 72 8.94 Example 9 TEAH 2 Glycerol 3 - - 95 9.89 Example 10 TMAH 5 Glycerol 32 - - 63 8.15 Example 11 TMAH 4 Glycerol 40 - - 56 7.49 Example 12 KOH 0.03 Glycerol 42 - - 57.97 2.15 Example 13 TEAH 9 Glycerol 2 - - 89 9.91 Example 14 TEAH 6 Glycerol 48 - - 46 7.48 Example 15 KOH 0.03 Glycerol 0.8 - - 99.17 9.52 Example 16 TEAH 12 Glycerol 52 - - 36 5.89 Example 17 KOH 0.03 Glycerol 52 - - 47.97 2.03 Comparative Example 1 TMAH 0.5 - - - - 99.5 12.67 Comparative Example 2 TMAH 0.5 - - A 0.1 99.4 10.02 Comparative Example 3 TMAH 0.5 - - A 2.0 97.5 2.62 Comparative Example 4 - - Glycerol 10.0 - - 90.0 1.51 Comparative Example 5 TMAH 0.5 MDG 19.4 A 0.1 80.0 5.92 Comparative Example 6 TMAH 0.5 NMP 17.5 A 2.0 80.0 1.94 Comparative Example 7 TMAH 0.5 - - D 19.5 80.0 5.82 Comparative Example 8 TMAH 0.5 EG 19.5 - - 80.0 5.18 TMAH: tetramethylammonium hydroxide
TEAH: tetraethylammonium hydroxide
KOH: potassium hydroxide
MDG: Diethylene glycol monomethyl ether
NMP: N-methylpyrrolidone
EG: ethylene glycol
A: methyl gallate
B: Succinic amide ester
C: silsesquioxane
D: Sorbitol

Experimental example 1: electrical conductivity measurement

After each of the compositions of Examples and Comparative Examples was prepared, electrical conductivity was measured using an electrical conductivity meter (Orion 5 Star) while maintaining 25°C. After immersing the electrical conductivity electrode in each of the detergent compositions, wait for the measurement to be completed, and then notify the measurement device display device of the measurement completion, and the values are recorded.

Experimental example 2: inorganic particles Removal power evaluation

An experimental sample was prepared so that silver particles were formed on the surface by forming a pattern on the substrate deposited with silver through wet etching. Count the number of silver particles formed in the 300 µm × 200 µm area in the sample through an optical microscope, and set each of the cleaning agent compositions prepared in the Examples and Comparative Examples at 25° C. at ^{1 kgf/cm 2 using a spray cleaner.} After treatment for 30 seconds while maintaining the same, the number of remaining particles was counted to evaluate the removal rate as shown in Equation 1 below, and the results are shown in Table 2 below.

[Equation 1]

Particle removal rate (%) = [(Number of particles remaining before composition treatment-Number of particles remaining after composition treatment)/(Number of particles before composition treatment)] × 100

Experimental example 3: Evaluation of stability over time

An experimental sample in which silver particles were formed was prepared in the same manner as in Experimental Example 2, and the number of silver particles in a region of 300 μm×200 μm was counted in the sample through an optical microscope. Using a spray cleaner, the cleaner was operated for 24 hours while maintaining each of the cleaner compositions prepared in Examples and Comparative Examples at 25°C at ^{1kgf/cm 2.} At this time, at the 10th and 24th hours of operation of the washing machine, the experimental sample was treated for 30 seconds, and the number of remaining silver particles was counted to evaluate the removal rate. At this time, the removal rate was calculated in the same manner as in Equation 1, and the results are shown in Table 2 below. By comparing the removal rate after 10 hours and after 24 hours, the degree of reduction in the removal rate over time, that is, stability over time was compared.

Experimental example 4: resorption evaluation

99.9% by weight of each detergent composition and silver powder (manufactured by Sigma Aldrich, 2 ~ 3.5㎛, 99.9% or more) prepared in the above Examples and Comparative Examples After mixing 0.1% by weight, it was dispersed for 30 minutes using a sonicator. An ITO single film was prepared, immersed in each of the detergent compositions in which the silver powder was dispersed for 5 minutes, washed with deionized water, and counted the number of silver particles re-adsorbed in the area of 300 µm × 200 µm on the ITO single film. The results are shown in Table 2 below.

Experimental example 5: corrosion Prevention power evaluation

Prepare a 2cm × 2cm substrate (thickness: 3000Å) on which an Al single layer was deposited, and immerse the substrate in the detergent composition for 10 minutes while maintaining the respective detergent compositions prepared in the Examples and Comparative Examples at 30°C. , The etching rate of the Al film was measured, and the results are shown in Table 2 below.

In addition, substrates on which Ti, Cu, and ITO films were deposited were prepared, and each of the prepared substrates was immersed in each of the detergent compositions for 30 minutes while maintaining each of the detergent compositions at a constant temperature of 30°C. Thereafter, each substrate was washed and dried with deionized water, and evaluated using a scanning electron microscope (SEM, Hitach S-4700), and the results are shown in Table 2 below. At this time, the evaluation criteria are as follows.

<Evaluation criteria>

◎: Very good (no corrosion)

○: Good (fine corrosion is present, but usable level)

△: Moderate (thickness change and lifting phenomenon observed)

×: Poor (thickness change and lifting phenomenon severe)

Experimental example 6: Organic film Invasiveness evaluation

A phenomenon in which a photoresist (manufactured by Dongwoo Finechem) is applied to a thickness of 1.2㎛ on a glass substrate, exposed by introducing a commonly known positive photoresist manufacturing method, and then immersed in a developer (manufactured by Dongwoo Finechem) for 30 seconds at room temperature. Through the process, patterning was performed to prepare an experimental sample. The prepared sample was immersed for 30 minutes while maintaining each of the detergent compositions prepared in Examples and Comparative Examples at 40°C, and then washed with deionized water and dried under a scanning electron microscope (SEM, Hitach S-4700). ) And the results are shown in Table 2 below. At this time, the evaluation criteria are as follows.

<Evaluation criteria>

◎: Very good (no change in thickness and no lift)

○: Good (thickness change is fine, but there is no lifting phenomenon)

△: Moderate (thickness change and lifting phenomena are finely observed)

×: Poor (thickness change and lifting phenomenon severely observed)

Inorganic particle removal rate (%) Inorganic particle removal rate after aging (%) Resorption Assessment (EA) Corrosion protection Organic film infringement 10hr 24hr Al E/R
(Å/min) Ti Ag ITO Example 1 91 93 92 92 32 ◎ ◎ ◎ ○ Example 2 94 93 93 98 41 ◎ ◎ ◎ ○ Example 3 91 91 92 95 39 ◎ ◎ ◎ ◎ Example 4 92 91 92 93 38 ◎ ◎ ◎ ◎ Example 5 90 90 91 107 37 ◎ ◎ ◎ ◎ Example 6 92 91 91 95 40 ◎ ◎ ◎ ◎ Example 7 92 93 92 110 35 ◎ ◎ ◎ ◎ Example 8 95 94 94 105 45 ◎ ◎ ◎ ◎ Example 9 94 95 94 82 55 ◎ ◎ ◎ ◎ Example 10 92 94 93 144 66 ◎ ◎ ◎ ◎ Example 11 93 93 92 158 61 ◎ ◎ ◎ ◎ Example 12 84 82 83 155 43 ◎ ◎ ◎ ◎ Example 13 93 92 92 99 92 ◎ ◎ ◎ ◎ Example 14 89 88 88 164 64 ◎ ◎ ◎ ◎ Example 15 85 82 84 149 158 ◎ ◎ ◎ ◎ Example 16 86 84 86 169 147 ◎ ◎ ◎ ◎ Example 17 82 83 82 165 42 ◎ ◎ ◎ ◎ Comparative Example 1 93 92 92 498 253 ◎ ◎ ◎ ◎ Comparative Example 2 92 93 91 516 189 ◎ ◎ ◎ ◎ Comparative Example 3 90 64 30 582 45 ◎ ◎ ◎ ◎ Comparative Example 4 0 0 0 389 6 ◎ ◎ ◎ ◎ Comparative Example 5 90 91 91 214 184 ◎ ◎ ◎ △ Comparative Example 6 85 65 25 512 48 ◎ ◎ ◎ × Comparative Example 7 91 25 0 552 64 ◎ ◎ ◎ ◎ Comparative Example 8 87 75 68 459 221 ◎ ◎ ◎ △

Referring to Table 2, in the case of Examples 1 to 17 including all of the configurations presented in the present invention, the inorganic particle removal rate and stability over time are better than Comparative Examples 1 to 8 not including any of the configurations presented in the present invention. It is excellent and has the advantage of minimizing re-adsorption of inorganic particles, and it has been confirmed that damage to the organic film is prevented by inhibiting corrosion of the metal corrosion film and preventing the composition from penetrating into organic matter.

Particularly, in the case of Examples 1 to 9 satisfying the most preferable range of each component presented in the present invention, it was confirmed that the above-described effects are most excellent.

Claims (6)

Alkali compounds; An organic solvent containing glycerol; And water; a cleaning agent composition for a semiconductor or display substrate containing. The method of claim 1,
The alkali compound is a detergent composition, characterized in that contained in an amount of 0.05 to 10% by weight, based on 100% by weight of the total composition containing the same. The method of claim 1,
The glycerol is a detergent composition, characterized in that contained in an amount of 1 to 50% by weight, based on 100% by weight of the total composition comprising the same. The method of claim 1,
The composition has an electrical conductivity of 2 to 10 mS/cm. The method of claim 1,
The detergent composition further comprises an organic solvent or a corrosion inhibitor other than glycerol. The method of claim 5,
The anti-corrosive agent is a cleaning agent composition, characterized in that it is contained in an amount of 0 to 5% by weight, based on 100% by weight of the total composition comprising the same.