TWI518467B - Photoresist stripper composition, electronic device and method of fabricating the same - Google Patents

Description

Photoresist remover and electronic component and method of manufacturing same

BACKGROUND OF THE INVENTION 1. Field of the Invention This invention relates to a photoresist removal agent, and more particularly to a photoresist removal agent containing a secondary or tertiary alcohol amine, a polar solvent, and an alcohol ether compound.

Generally, the process of the semiconductor integrated circuit is basically performed by: forming a material layer on the substrate; coating the photoresist on the material layer; selectively exposing and developing the photoresist to form a pattern; The photoresist layer is used as a mask, and the material layer is etched to transfer the microcircuit pattern to the lower photoresist layer. Finally, the photoresist layer is removed using an photoresist stripper.

For photoresist strippers, their high stripping capacity and low corrosivity are two basic requirements. The high stripping capability ensures that no photoresist material remains on the substrate after rinsing; while low corrosivity is to avoid damage to the underlying metal or dielectric material of the photoresist. In addition, the photoresist stripping agent may additionally require characteristics such as high temperature stability, low volatility, storage stability, and low toxicity.

The invention provides a photoresist removing agent which can remove photoresist under the photoresist The layer material maintains good corrosion resistance. The present invention further provides a method of manufacturing an electronic component using such a photoresist remover to remove photoresist on a substrate, and an electronic component produced by the manufacturing method.

The photoresist removing agent of the present invention comprises a polar ether compound represented by Formula 1, an polar solvent selected from the group consisting of a compound represented by Formula 2, a compound represented by Formula 3, and a mixture thereof, and at least one compound represented by Formula 4. a secondary alcohol amine or at least one tertiary alcohol amine: Wherein n is an integer from 1 to 3; R ₁ is C ₁ -C ₄ alkyl; R _{2 is} independently hydrogen or methyl; X ₁ and X ₂ are C ₁ -C ₄ alkyl, C ₂ -C ₄ extends alkenyl, >R _x -COOH or >R _y OH, wherein R _x is a C ₁ -C ₃ linkage, R _y is a C ₁ -C ₄ linkage; R ₃ is H, C ₁ -C ₄ alkyl or -R _z OH, wherein R _z is a C ₁ -C ₄ linking group; R ₄ and R ₅ are each a C ₁ -C ₄ alkylene group, and Y ₁ and Y ₂ may be H or -OH, respectively. .

In one embodiment of the invention, the amount of water in the photoresist remover is less than 10% by weight.

In one embodiment of the invention, the photoresist remover comprises a tertiary alcohol amine, an alcohol ether The compound and the polar solvent, and the water content in the photoresist remover is less than 10% by weight.

In one embodiment of the present invention, the secondary alcohol amine or the tertiary alcohol amine accounts for 1% by weight to 20% by weight, and the alcohol ether compound accounts for 25% by weight to 50% by weight based on the total amount of the photoresist removing agent. The polar solvent accounts for 30% by weight to 70% by weight.

In one embodiment of the invention, the polar solvent is propylene carbonate, propylene glycol or a mixture thereof.

In one embodiment of the invention, the secondary alcohol amine is N-methyl ethanolamine (NMEA), N-ethylethanolamine or a mixture thereof.

In one embodiment of the invention, the tertiary alcohol amine is triethanolamine (TEA), dimethylethanolamine (DMEA), 1-(2-hydroxyethyl)piperazine (1-(2-hydroxyethyl) ) piperazine) or a mixture thereof.

In one embodiment of the invention, the alcohol ether compound is diethylene glycol monobutyl ether (BDG), dipropylene glycol methyl ether (DPM) or a mixture thereof.

The method of manufacturing an electronic component of the present invention comprises removing a photoresist formed on a substrate using the above-described photoresist removing agent, wherein a structure including aluminum, copper, molybdenum or an indium-containing oxide is formed on the substrate.

The electronic component of the present invention is produced by the aforementioned method of manufacturing an electronic component.

Based on the above, the present invention proposes a photoresist stripping agent which penetrates a secondary alcohol amine or a tertiary alcohol amine, an alcohol ether compound, and a diol compound or a lactone compound to achieve excellent photoresist removal. Ability, and effectively inhibit the effect of corrosion of materials.

The above described features and advantages of the present invention will be more apparent from the following description.

In the present specification, the range represented by "a value to another value" is a schematic representation that avoids enumerating all the values in the range in the specification. Therefore, the recitation of a particular range of values is intended to include any value in the range of values and the range of values defined by any value in the range of values, as in the specification. The scope is the same. For example, in the range of "20 to 80% by weight", the range of "30 to 50% by weight" is covered regardless of whether other values are listed in the specification.

A first embodiment of the present invention proposes a photoresist removing agent containing an alcohol ether compound, a polar solvent, and a secondary alcohol amine or a tertiary alcohol amine. When the photoresist is removed using the photoresist removal agent of the first embodiment, the alcohol amine reacts with the photoresist material, and the reacted photoresist material is removed by the interaction of the polar solvent and the alcohol ether compound. These three components will be detailed separately below.

In the present embodiment, the alcohol ether compound is represented by Formula 1: Wherein n is an integer from 1 to 3; R ₁ is a C ₁ -C ₄ alkyl group; and R _{2 is} each independently hydrogen or methyl.

For example, the alcohol ether compound may be 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, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether or any combination of the foregoing compounds, but is not limited thereto.

In a specific embodiment of the invention, the alcohol ether compound is diethylene glycol monobutyl ether (BDG) or dipropylene glycol methyl ether (DPM).

In the present embodiment, the polar solvent is selected from the group consisting of the compound represented by Formula 2, the compound represented by Formula 3, and a mixture thereof: Wherein X ₁ and X ₂ are C ₁ -C ₄ alkylene, C ₂ -C ₄ alkylene, >R _x -COOH or >R _y OH, wherein R _x is a C ₁ -C ₃ linkage, R _y is a C ₁ -C ₄ linking group.

The compound represented by Formula 2 can be reduced to the compound represented by Formula 3 under an alkaline environment. In this regard, X ₁ and X ₂ may be the same group.

For example, the compound represented by Formula 3 may be propylene glycol (PG), which may be regarded as a product of a reaction of propylene carbonate and an alcohol amine. Accordingly, a specific example of the compound represented by Formula 2 may be propylene carbonate (Propylene). Carbonate, PC).

As for the secondary alcohol amine or the tertiary alcohol amine, it can be represented by the formula 4: Wherein R ₃ is H, C ₁ -C ₄ alkyl or -R _z OH, R _z is a C ₁ -C ₄ linkage; and R ₄ and R ₅ are respectively C ₁ -C ₄ alkyl, Y ₁ and Y ₂ may be H or -OH, respectively, with the constraint that at least one of R ₃ , Y ₁ and Y ₂ contains -OH.

For example, the secondary alcohol amine may be N-methylethanol amine, N-ethylethanolamine, diethanolamine or any combination of the foregoing compounds; and the tertiary alcohol amine may be triethanolamine (triethanolamine, TEA), dimethylethanolamine (DMEA), diethylethanolamine, methyldiethanolamine, N-methyldiethanolamine or 1-(2-hydroxyethyl)piperazine (1-(2-hydroxyethyl)piperazine Or any mixture of the foregoing compounds, but is not limited thereto.

In a particular embodiment of the invention, the secondary alcohol amine is N-methylethanolamine; the tertiary alcohol amine is triethanolamine, dimethylethanolamine or 1-(2-hydroxyethyl)piperazine.

The inventors have found that when a compound represented by Formula 2 or Formula 3 is used in combination with a secondary or tertiary alcoholamine, it provides a good photoresist removal effect, and when removing the photoresist, aluminum, copper, molybdenum or The degree of corrosion of indium containing oxides is very low. The following <Experiment> section will further prove it.

In an embodiment of the invention, the secondary alcohol amine or the tertiary alcohol amine accounts for 1% by weight to 20% by weight, and 4% by weight to 10% by weight, based on the total amount of the photoresist removing agent. good. The alcohol ether compound accounts for 25% by weight to 55% by weight, and more preferably 35% by weight to 50% by weight. The polar solvent accounts for 30% by weight to 70% by weight, and preferably 40% by weight to 55% by weight.

Further, although the photoresist removal agent of the first embodiment has a small degree of corrosion of the material, the present invention does not thereby exclude the application of the corrosion inhibitor. For example, corrosion inhibitors such as azoles, organic phenols or sugar alcohol compounds can still be added to the photoresist remover.

It is also worth noting that the photoresist removal agent of the first embodiment may contain only a small amount of water, such as less than 15% by weight, less than 10% by weight, less than 7% by weight, or even less than 5% by weight. . Alternatively, the photoresist remover may be a non-aqueous, non-aqueous photoresist remover. The inventors have found that a small addition of water contributes to the removal of the photoresist, but as the amount of water increases, the alcoholamine is activated to increase the corrosiveness to the metal; and at the same time, the proportion of the polar solvent is relatively reduced so that the photoresist The ability to remove becomes poor.

A second embodiment of the present invention proposes a method of manufacturing an electronic component and an electronic component manufactured by the manufacturing method. The electronic component is not particularly limited, and an important point is that, in the manufacturing process, after forming a certain material layer, the photoresist removing agent of the first embodiment is used to remove the residual photoresist of the upper layer of the material layer. Among them, this method is particularly suitable for the case where the material layer contains copper, aluminum, molybdenum or a transparent conductive oxide such as indium oxide.

<experiment>

The present invention will be more specifically described below with reference to experimental examples. Although the following experiments are described, the materials used, the amounts and ratios thereof, the processing details, the processing flow, and the like can be appropriately changed without departing from the scope of the invention. Therefore, the invention should not be construed restrictively based on the experiments described below.

In Experiments 1 to 5, the inventors prepared a variety of photoresist removers, and tested the photoresist removal capabilities of these photoresist removers, and their corrosion rates for different materials, the results are summarized in Table 1 to table 5. Among them, the evaluation criteria of the photoresist removal ability is: after cleaning the substrate with a photoresist remover, the substrate is observed by a scanning electron microscope, and a significant photoresist residue is observed as X at a magnification of 4 k; at a magnification of 20 k It was observed that the apparent residue was judged as Δ; at the magnification of 20 k, no significant residue was observed to be judged as ○. As for the measurement of the corrosion rate of the material, the glass substrate containing the metal wiring (material such as Cu, Mo, Al or alloy thereof) was immersed at a fixed temperature of 20 ° C for 20 minutes. Observe and measure the concentration of dissolved metal ions in the test solution as a basis for comparison.

In addition, the full abbreviations used in the table are detailed below.

Experiment 1 (Experimental Examples 1-1 to 1-4 and Comparative Examples 1-1 to 1-2)

Experiment 1 is basically an experimental result obtained by changing the polar solvent component in the photoresist remover. It can be seen from Table 1 that the experimental examples 1-1 and 1-2 using propylene carbonate as a polar solvent have the effects of photoresist removal ability and corrosion of materials (especially Zn in Cu and IGZO). It is superior to Comparative Examples 1-1 and 1-2 using NMF or NMP as a polar solvent.

Further, Experimental Examples 1-3 and 1-4 also used propylene carbonate as a polar solvent, but a corrosion inhibitor was further added to the photoresist remover. Therefore, its effect of suppressing corrosion is better. However, comparing Experimental Examples 1-1, 1-2 and Experimental Examples 1-3, 1-4, it was found that the photoresist removal agent can achieve almost the same corrosion inhibiting effect even without the addition of a corrosion inhibitor. This confirmed the superior effect of the combination of propylene carbonate, alcohol ether compounds and tertiary alcohol amines.

Experiment 2 (Experimental Examples 2-1 to 2-2 and Comparative Example 2-1)

Experiment 2 is an experimental result obtained by changing the alcohol amine component in the photoresist remover. It can be seen from Table 2 that even if propylene carbonate is also used as the polar solvent, when the use of the alcoholamine is a non-tertiary alcohol amine, there is a high corrosion condition to the copper metal wiring, and the use of the tertiary alcohol amine is used. Underneath, the corrosion of the copper wiring is substantially slight.

Experiment 3 (Experimental Example 3-1 and Comparative Example 3-1)

Experiment 3 is an experimental result for a photoresist remover containing a secondary alcohol amine. Since the reactivity of the secondary alcohol amine to copper is stronger than that of the tertiary alcohol amine, the corrosion rate of copper in this experiment is higher than that of the previous experiments using the tertiary alcohol amine. Nevertheless, it can be seen from Table 3 that when propylene glycol is used as the polar solvent (Experimental Example 3-1), the effect of the photoresist removing agent on suppressing the corrosion phenomenon is still superior to Comparative Example 3-1 using NMF as the polar solvent. This indicates that propylene glycol is also a suitable polar solvent choice.

Experiment 4 (Experimental Examples 4-1 to 4-2 and Comparative Examples 4-1 to 4-4)

Experiment 4 was conducted using propylene carbonate or propylene glycol as a polar solvent to test the experimental results of adding different amounts of water to the photoresist remover. As can be seen from Table 4, when the water content is only 7% by weight, the corrosion rate of each material is kept constant regardless of whether the polar solvent is propylene carbonate (Experimental Example 4-1) or propylene glycol (Experimental Example 4-2). Within the low range, once the amount of water added is higher than 15% by weight, the corrosion rate of copper increases immediately, and the etching rate of IGZO is also greatly increased, and at the same time, the proportion of polar solvent is relatively decreased so that light The ability to remove the barrier becomes poor.

In summary, the present invention provides a photoresist stripping agent which is excellent in the interaction of a secondary alcohol amine or a tertiary alcohol amine, an alcohol ether compound, and a lactone compound or a glycol compound. The photoresist removal ability is effective and the effect of corrosion of the material is effectively suppressed. The photoresist stripping agent can eliminate the need to add a corrosion inhibitor, thereby facilitating the recycling of the photoresist stripper after use.

Although the present invention has been described above by way of examples, it is not intended to limit the invention. Any changes and modifications may be made without departing from the spirit and scope of the invention. Therefore, the scope of protection of this application is subject to the definition of the scope of the patent application attached.

Claims (8)

A photoresist removal agent comprising: an alcohol ether compound represented by Formula 1; a polar solvent selected from the group consisting of a compound represented by Formula 2, a compound represented by Formula 3, and a mixture thereof; and at least one secondary alcohol amine Or at least one tertiary alcohol amine, represented by Formula 4; Wherein n is an integer from 1 to 3, R ₁ is C ₁ -C ₄ alkyl, R _{2 is} independently hydrogen or methyl, and X ₁ and X ₂ are C ₁ -C ₄ alkyl, C ₂ - C _{4 is} an alkenyl group, >R _x -COOH or >R _y OH, wherein R _x is a C ₁ -C ₃ linking group, R _y is a C ₁ -C ₄ linking group, and R ₃ is H, C ₁ -C ₄ An alkyl group or -R _z OH, wherein R _z is a C ₁ -C ₄ linking group, R ₄ and R ₅ are each a C ₁ -C ₄ alkylene group, and Y ₁ and Y ₂ are each H or -OH, wherein The secondary alcohol amine or the tertiary alcohol amine accounts for 1% by weight to 20% by weight based on the total amount of the photoresist removing agent, and the alcohol ether compound accounts for 25% by weight to 50% by weight, and the polar solvent accounts for 30% by weight to 70% by weight. The photoresist remover according to claim 1, wherein the water content is less than 10% by weight. The photoresist removal agent according to claim 1, which comprises the tertiary alcohol amine, the alcohol ether compound and the polar solvent, and the water content of the photoresist remover is less than 10% by weight. The photoresist remover according to any one of claims 1 to 3, wherein the polar solvent is propylene carbonate, propylene glycol or a mixture thereof. The photoresist remover according to claim 1, wherein the secondary alcohol amine is N-methylethanolamine, N-ethylethanolamine or a mixture thereof. The photoresist remover according to claim 1, wherein the tertiary alcoholamine is triethanolamine, dimethylethanolamine or 1-(2-hydroxyethyl)piperazine or a mixture thereof. The photoresist remover according to claim 1, wherein the alcohol ether compound is diethylene glycol butyl ether or dipropylene glycol methyl ether. A method of manufacturing an electronic component comprising: removing a photoresist formed on a substrate by using a photoresist removal agent of claim 1 wherein a structure including aluminum, copper, molybdenum or indium oxide is formed on the substrate .