TW201118511A - Stripper composition for photoresist and method for stripping photoresist - Google Patents

Abstract

The present invention relates to a photoresist stripper composition. More particularly, the photoresist stripper composition according to the present invention has excellent photoresist stripping ability and excellent corrosion prevention effect in respects to a lower film of photoresist in the case of when molybdenum (Mo) is comprised in the lower film of photoresist by comprising a compound that is represented by Formula 1.

Description

201118511 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a photoresist peeling composition and a peeling resist method using the same. [Prior Art] The microcircuit process of a semiconductor integrated circuit or a liquid crystal display is performed by the following steps: uniformly coating a photoresist on a film formed on a substrate, such as a conductive metal film (e.g., a conductive metal film) Aluminum, aluminum alloy, copper, steel alloy, molybdenum, molybdenum alloy and the like), ruthenium oxide film, tantalum nitride film and the like; selectively exposing and developing the photoresist to form a photoresist pattern; Using a patterned photoresist film as a mask, performing a wet or dry (four) on the conductive metal film or the insulating film, and then transferring the microcircuit pattern to the lower layer of the photoresist; and using a stripping agent (peeling solution) to remove unnecessary photoresist Layer removal. The basic characteristics required to manufacture a semiconductor device and a liquid crystal display for removing the photoresist from the photoresist will be described below. First, the photoresist must be stripped at a low temperature for a short period of time and should exhibit excellent _ force. After rinsing, no ruthenium residue remains on the substrate. : Xi Bu: Must have low corrosion resistance to avoid the metal film or the damage of the lower layer of the photoresist. In addition, if there is an interaction between the solvents constituting the release agent = the storage stability of the release agent may be problematic, and the 'order change' when the release agent is made may exhibit different characteristics, so the mixed solvent should not start... And should have high temperature stability. Furthermore, consideration should be given to the environmental aspects of workers or environmental issues of waste disposal, which should be low in toxicity. In addition, * 201118511 When the photoresist is peeled off at a high temperature, if a large amount of volatilization occurs, the composition ratio will be rapidly changed to k, and the stability and operational reproducibility of the release agent will be lowered. Accordingly, it should have low volatility. In addition, a predetermined amount of the stripper should be capable of processing a plurality of substrates, the components constituting the stripper should be easily supplied, the components should be inexpensive, and the waste stripper should be reprocessed after treatment to ensure economic efficiency. In order to satisfy these conditions, various photoresist peeling compositions have been developed. However, there is still a need to develop a photoresist stripping composition which does not react with other components in the composition, does not produce by-products, and has low corrosivity which does not cause damage to the metal film or the insulating film of the lower layer of the photoresist, so as to be more excellent. The photoresist peels off the composition. SUMMARY OF THE INVENTION An object of the present invention is to provide a photoresist release composition which has an excellent photoresist peeling effect and which does not corrode a photoresist under the photoresist peeling step. In particular, it is an object of the present invention to provide a photoresist stripping composition which can effectively strip a photoresist and which does not cause corrosion of the underlayer film when the lower layer of the photoresist is a multilayer film of a copper film/molybdenum film. In order to achieve the above object, the present invention provides a photoresist stripping composition comprising: a compound represented by the following formula 1; and 2) a solvent. [Formula 1]

, R HN,

N-R"—〇H 201118511 wherein R ' R' and R′′ are the same or different and each independently is a linear or branched alkylene group having 1 to 6 carbon atoms. Further, the present invention provides A method of peeling off a photoresist using a photoresist stripping composition. The photoresist stripping composition of the present invention has excellent photoresist peeling speed and peeling efficiency 'and has excellent corrosion resistance to a photoresist lower layer. The present invention will be described in detail. With the development of high resolution and large screen display, copper (fU) circuits with low impedance are necessary. In the case of Cu, 'because of its low strength to glass and its The case of diffusion to the underlayer film is severe. Therefore, other gold > 1 film is required as a diffusion preventive film. Recently, a Cu alloy using a double film structure (which uses a molybdenum (Mo) alloy) is used. In the case of the alloy, since the deposition device may have particle stagnation, for example, particle contamination of the Τ granules often occurs, the yield is lowered, and the cost of the port is still high. When Mo is used instead of the bismuth alloy as the lower layer, Will be connected to Cu At the place where electric light is combined (suppressing 仏 仏 c (4), when using a high/alkali-based photoresist stripper, it may cause a lot of corrosion. Accordingly, since the photoresist stripper will cause rot (4), it is not used by the company. η·. As a lower layer of photoresist. However, since the photoresist stripping composition of the present invention includes the compound of Formula 1, it can solve the problem of underlayer corrosion of the photoresist, and is superior to the conventional organic amine compound. In the prior art, when the thickness of the Mo film is below i〇nm, since the galvanic phenomenon is quite serious, it is impossible to use the photoresist stripping composition, but in the present invention, when M When the thickness of the ruthenium film is less than nm, the photoresist peeling composition of the present invention can still be used. Further, if a smear occurs in the process, the corrosion phenomenon becomes augmented as the number of times of the photoresist stripping step increases during repeated operations. More serious, and waste disposal should be carried out. However, in the present invention, when the photoresist peeling step is repeated several times, repeated operations can be performed because corrosion problems do not occur. The photoresist stripping composition comprises: a compound of the formula i; and 2) a solvent. In the formula 1, R is preferably a methylene group, and R is a subfilament having two or more carbon dimers. More preferably, it is an ethylene group. A preferred structural formula of the compound is shown in the following formula 1-1. [Formula 1-1]

Wherein R" is a linear or branched alkylene group having a preferred formula 1-1 [formula 1-2] 丨 to 6 carbon atoms. The compound shown is represented by the following formula 1-2.

Preferably, the boiling point of the formula (b.p.). The compound of the formula has 54 to 58 eC/3.3 Torr 201118511. The compound of the formula 1 can be prepared by a method comprising 'jumping (R〇) n (where R is from 1 to 6 carbons) The compound of the formula 2 is refluxed in the presence of a solvent and in the presence of a solvent. [Formula 2] H2N-R'-MH-R,, -〇h wherein R and R" are the same Or different, each of which is independently a linear or branched group having from 1 to 6 carbon atoms. In the above, preferably, R is a methylene group, and R and R" are ethylene (ethylene). And η is in the above method, and the solvent is not particularly limited, and may be, for example, an alcohol such as benzene, preferably methanol. In the above, the reactants may be heated to reflux. The reflow temperature can be easily determined in the art according to the boiling point of the solvent. For example, when the solvent t is present, it is hungry than the 85 1st. The reflux time is preferably from 3 minutes to 2 hours, more preferably about one hour. The above method can be carried out under normal atmospheric pressure. A detailed example of the production method is shown in Reaction Scheme 1. [Reaction formula 1]

HN Μ

H2N Benzene (?) ν'?'0? The compound represented by the total weight of the whole composition is preferably from 1 to 35 wt% or more, more preferably from 3 to 3 G. If the content of the organic amine compound is less than 丨wt%, the peeling force against the deteriorated photoresist will be 'when the content is higher than 35 Wt%' due to the viscosity increase, the photoresist penetration is lower, and the material is prolonged, and It will increase the conductivity of the conductive layer 201118511 gold layer film. In addition to the compound of Formula 1, the photoresist release composition of the present invention may further comprise an organic amine compound as known in the art. More specific examples are monoethanolamine (MEA), 1-aminoisopropanol (AIP), 2-amino-1-propanol, N-methylaminoethanol (N-MAE), 3- Amino-l-propanol, 4-amino-1-butanol, 2-(2-aminoethoxy)-1-ethanol (AEE), 2-(2-aminoethylamino)-1 -2-(2-aminoethylamino)-l-ethanol, diethanolamine (DEA), triethanolamine (TEA), and hydroxyethylpiperazine (HEP), but are not limited thereto. In the photoresist stripping composition of the present invention, when it further comprises an organic amine compound, the total amount of the compound represented by Formula 1 and the organic amine compound is preferably from 1 to 35 wt%, preferably more than the total weight of the total composition. It is 3 to 30 wt〇/. . In the photoresist release composition of the present invention, 2) the solvent has excellent compatibility with water and an organic compound, and is a solvent for dissolving a photoresist. In addition, & reduces the surface tension of the release agent to increase the wettability to the photoresist film. A solvent known in the art can be used as the 2) solvent. Specific examples are N-methylpyrrolidone (NMP), 1,3-dimethyl-2-imidazolidinone (DMI), dimercaptosulfoxide (DMSO), dimercaptoacetamide (DMAc), two Methyl amide (DMF), N-methylformamide 'NMF' 'tetramethylenesulfone, butyl diglycol (BDG), ethyl diglycol (EDG), hydrazine Diethylene glycol (MDG), triethylene glycol (TEG), diethylene glycol monoethyl ketone (DEM), diethylene glycol monobutyl ether, and mixtures thereof, but are not limited thereto. Based on the total weight of the overall composition, 2) the solvent content range is preferably 201118511 from 65 to 99 wt. / ® t/〇' is preferably from 7 to 97 wt%. If the solvent content is less than 65 Wt/°, the viscosity of the 1J stripper will increase, and the peeling force of the stripper may be lowered. The photoresist stripping composition of the present invention may further comprise one or more anticorrosive agents selected from the group consisting of compounds represented by the following formulas 3, 4, 5, 6 and 7: [Formula 3] R3

R2; wherein R1 is hydrogen, a thiol group having 1 to 12 carbon atoms, a thiol group or a hydroxyl group; and R2 is a hydrogen group having an alkyl group having 12 to 20 carbon atoms, an alkoxy group or having 6 to 20 carbon atoms An aryl group; R3 is hydrogen, an alkyl group having from 丨 to 12 carbon atoms, an alkoxy group or a hydroxyl group. As benzopyrene. The benzimidazole-based compound is benzoimidazole, 2-hydroxybenzimidazole, 2-methylbenzimidazole, 2-(hydroxymethyl) benzopyrimidine. 2-(hydroxymethyl)benzimidazole, 2-mercaptobenzimidazole and the like, preferably benzotriazole or 2-(hydroxymethyl)benzimidazole 1 but Not limited to this. [Formula 4] 201118511 R4^V\\ I! ,n

\_/RS N\ R6 ; Its Yin R4 is an alkyl group having 1 to 4 carbon atoms; and R6 is the same or different and each independently is a hydroxyalkyl group having 1 to 4 carbon atoms. [Formula 5]

Wherein R7 is a gas or an alkyl group having 1 to 4 carbon atoms. [Equation 6]

Wherein R8 is hydrogen or an alkyl group having from 丨 to 4 carbon atoms. [Formula 7] /,

OH

R11^^\Ri〇201118511 R9 and R10 are the same or different, each independently hydrogen or hydroxyl; R11 is hydrogen, tert-butyl, carboxylic acid (-COOH), methyl ester (-COOCH3), B Ester group (_C00C2H5) or butyl ester group (-(:00(:3Η7). In the photoresist stripping composition of the present invention, the content of the anticorrosive agent is preferably 0.01 to the total weight of the whole composition. 5 wt%, preferably 0.1 to 1 wt〇 /. If the anti-corrosion button content is less than 〇〇丨wt%, when the substrate to be separated is in contact with the stripping solution for a long time, the metal line will partially corrode. In the case where the content is more than 5% by weight, the peeling force is lowered due to an increase in viscosity, and the effect with respect to cost is poor in performance due to an increase in the cost of the composition. The photoresist stripping composition of the present invention has excellent light. It resists peeling force and exhibits excellent corrosion resistance to the conductive metal film or insulating film of the lower layer of the photoresist, and does not damage the conductive metal film or the insulating film of the lower layer of the photoresist. The conductive metal film or the insulating film may be a single layer. a film or a multilayer film of two or more layers including a metal such as aluminum or copper , 铉 or molybdenum) or a metal alloy. More preferably, the conductive metal film or the insulating film may be a single layer film or a multilayer film of two or more layers including a junction, copper or an alloy thereof; or a single layer film or two or more layers a multilayer film comprising copper or an alloy thereof and bismuth, molybdenum or alloy thereof. The stripping photoresist method of the present invention is characterized in that the photoresist stripping composition of the present invention is used. Step: Γ) coating the light jtj on the conductive metallographic or insulating film formed on the substrate = on the substrate; 3) using the patterned photoresist as a mask, like a conductive metal film or an insulating film; And 4) using the photoresist stripping of the present invention (four) 12 201118511 article 'peeling photoresist. The stripping resist method according to an embodiment of the invention comprises the steps of: 1) applying a photoresist to the entire surface of the substrate; 2) forming a photoresist pattern on the substrate; 3) forming a conductive metal film or an insulating film thereon. On the substrate having the photoresist pattern, and 4) using the photoresist stripping composition of the present invention, the photoresist is stripped. In the method of stripping photoresist of the present invention, the conductive metal layer or the insulating layer may be a single layer film or a multilayer film of two or more layers including a metal (e.g., aluminum, copper, titanium or turn) or a metal alloy. In detail, an Al-Nd/Mo bilayer film and a Cu/Mo bilayer film are preferable. The method of immersing (simultaneously immersing a plurality of substrates to be stripped in a large amount of stripping solution) and individual processing methods (spraying the stripping solution one by one onto the substrate to remove the photoresist) may be used. The photoresist stripping composition of the invention peels off the photoresist from the substrate on which the microcircuit pattern is formed. The types of photoresists which can be peeled off by using the photoresist stripping composition of the present invention are positive-type photoresists, negative-type photoresists, and positive/negative double-type photoresists, but the composition thereof is not limited thereto. However, particularly effective photoresists are photoresists including photosensitive compounds (based on phenolic resin and diazonaphthoquinone). A liquid crystal display or a semiconductor device obtained by stripping a photoresist using the photoresist stripping composition of the present invention has a small amount of residual light resistance, and the substrate having the micro pattern is not damaged or broken when the photoresist is peeled off. As described above, in the present invention, the photoresist film which is deteriorated in the etching process can be easily removed at a high temperature and a low temperature for a short time, and the present invention provides a photoresist 13 201118511 peeling composition 'the pair of conductive film and insulating film ( Such as aluminum or aluminum alloy, copper or copper alloy, or key or molybdenum alloy) has low corrosivity. The preferred embodiments are described in detail below to better understand the present invention. However, the following examples are merely illustrative of the invention, and the scope of the invention is not limited thereto. <Examples><Preparation Example > Preparation of an organic amine compound The compound represented by the formula 丨-2 was obtained according to the reaction formula 1. At this time, the reaction temperature was 85 to 95 ° C under normal pressure, and the reflux time was 1 hour. The physical properties of the resulting compound are as follows, and nuclear magnetic resonance (NMR) data are shown in Figures 1 and 2. Chemical formula: C5H12N20 Mass: 116.09 Molecular weight: 116.16 m/e: 1 16.09 (100.0%), 117.10 (5.6%) C, 51.70; Η, 10.41; Ν? 24.12; Ο, 13.77 <Examples 1 to 2> The composition and composition ratio shown in Table 1 were prepared, and the stripping solution was prepared. The composition was stirred at room temperature for 2 hours, and filtered with a 〇·1 μιη filter paper. <Comparative Examples 1 to 3> A stripping solution was prepared by the same method as in Examples 1 to 2 using the components and composition ratios shown in Table 1 below. 14 201118511 [Table l] Ingredients (parts by weight) Amine compound solvent Corrosion inhibitor group type Content Type Content Content (% by weight) (% by weight) (% by weight) Example 1 NMF 45 THBTA 0.1 IME 5 BDG 49.3 Bzl 0.6 Example 2 NMF 45 THBTA 0.1 IME 5 BDG 49.3 Bzl 0.6 NMF 45 THBTA 0.1 Comparative Example 1 AEE 5 BDG 49.3 Bzl 0.6 NMF 45 THBTA 0.1 Comparative Example 2 HEP 5 BDG 49.3 Bzl 0.6 NMF 45 THBTA 0.1 Comparative Example 3 NMEA 5 BDG 49.3 Bzl 0.6 AEE : aminoethoxyethanol HEP : via ethyl 0 IME : 1-σidazolidine ethanol NMEA : N-methylethanolamine BDG: II Diethylene glycol mono butyl ether NMF : N-methylformamide THBTA : Tetrahydrobenzotriazole Bzl: stupid and rice bran (benzimidazole) &lt Experimental Example > 15 201118511 1) Evaluation of Peeling Speed Using the Example 1 and Comparative Example 'Step of Stripping Resistivity (light hard baking for 5 minutes), the measurement was completely peeled off in the following table. 2 and Figure 3. The photoresist stripping composition prepared from 1 to 3 is resistant to 14 (TC, 15 〇艽 and 16 〇t: time required for photoresist). The evaluation results show [Table 2] Peeling time (seconds) ----- π 140 c Η/Β 150°C WB~~ 160°CH/B Example 1 10 10 ~' 30 寊 Example 2 10 10 ' 20 Comparative Example 1 10 75-- Too Comparative Example 2 10 70 200 Comparative Example 3 10 50 120 It can be seen from the results of Table 1 and Figure 3 that the photoresist stripping composition of the present invention has excellent peeling force and rapid peeling speed. 2) Evaluation of corrosion degree Using Example 1 and Comparative Examples 1 to 3 The photoresist peeling composition was subjected to the photoresist stripping step, and the degree of corrosion of the surface, side surface, and cross section of the sample was observed. The results are shown in Table 3 below. Here, the degree of carrion is evaluated by the following criteria. ® : No corrosion on the surface and side 〇: Some corrosion on the surface and side △: Partial corrosion on the surface and side surface 201118511 X: Severe corrosion on the entire surface and side [Table 3]

Photoresist underlayer film Mo/AINd Mo/Al Cu/MoTi Cu/Mo Example 1 ® Example 2 ® ® Comparative Example 1 XX Comparative Example 2 Δ ® Δ Comparative Example 3 〇 XX It can be found from Table 3, regardless of the lower layer of the photoresist What is the type of film, the photoresist composition of the present invention has excellent corrosion resistance. BRIEF DESCRIPTION OF THE DRAWINGS FIGS. 1 and 2 are NMR data charts of the compounds represented by Formula 1-2. Fig. 3 is a graph showing the results of evaluation of the peeling speed of the amine compound of the photoresist peeling composition. [Main component symbol description] None 0 17

Claims (1)

201118511 VII. Patent Application Range·· h—A photoresist stripping composition, including: 1)—a compound represented by the following formula 1; and 2) a solvent, [Formula 1], κ ΗΝ: N~R" —〇Η R. wherein R, R′ and R′′ are the same or different and are each independently a straight or branched alkylene group having from 1 to 6 carbon atoms. 2. As described in claim 1 The photoresist peeling composition, wherein the compound represented by Formula 1 is a compound represented by the following formula 1_丨, [Formula 1-1] Wherein R" is a linear or branched alkylene group having 1 to 6 carbon atoms. 3. The photoresist stripping composition according to claim 1, wherein the compound of the formula 1 is Compound shown in 丨_2, [Formula 1-2] 4. The photoresist stripping composition of claim 1, wherein ^' is based on the total weight of the composition, and the compound is represented by Formula 1 in an amount ranging from 1 to 35 wt%. 18 201118511 5. The photoresist stripping composition of claim 1, further comprising: one or more organic amine compounds selected from the group consisting of monoethanolamine (MEA), 1-aminoisopropanol (AIP), 2-Amino-1-propanol, N-methylaminoethanol (N-MAE), 3-amino-1-propanol, 4-amino-1-butanol, 2-(2 -Aminoethoxy)-1-ethanol (AEE), 2-(2-aminoethylamino)-l-ethanol, diethanolamine (DEA) ), triethanolamine (TEA) and a group consisting of hydroxyethylpiperazine (HEP). 6. The photoresist stripping composition of claim 1, wherein 2) the solvent comprises a group selected from the group consisting of N-mercaptopyrrolidone (NMP) and 1,3-dimercapto-2-imidazolidinone ( DMI), dimercaptosulfoxide (DMSO), dimercaptoacetamide (DMAc), dimethylformamide (DMF), N-methylformamide (NMF), cyclobutene (tetramethylenesulfone), butyl diglycol (BDG), ethyl diglycol (EDG), decyl diglycol (MDG), triethylene glycol (TEG), diethylene glycol monoethyl ether (DEM), diethylene glycol One or more of the group consisting of monobutyl ether and mixtures thereof. 7. The photoresist stripping composition of claim 1, wherein the solvent content ranges from 65 to 99 wt% based on the total weight of the composition. 8. The photoresist stripping composition according to claim 1, further comprising: one or more anticorrosive agents selected from the group consisting of compounds represented by the following formulas 3, 4, 5, 6 and 7: [Formula 3] 201118511 R3 R1 R2 wherein, hydrogen is an alkyl group having 1 to 12 carbon atoms, a thiol group or a hydroxyl group R2 is hydrogen, an alkyl group having from 1 to 12 carbon atoms, an alkoxy group or having 6 to 20 carbon atoms Aryl, R3 is a gas, a fluorenyl group; [Formula 4], /, an alkyl group having 1 to 2 carbon atoms, an alkoxy group or a hydroxy group, R5 N, R6 which makes R 4 hydrogen, having 1 to An alkyl group of 4 carbon atoms, R5 and R6 being the same or different 'each independently being a hydroxyalkyl group having 1 to 4 carbon atoms; [Formula 5] 20 201118511 wherein R7 is hydrogen or an alkyl group having from ～4 carbon atoms; [Formula 6] R8- Wherein R8 is hydrogen or an alkyl group having from 丨 to 4 carbon atoms; [Formula 7] OH R9 R10 R11 wherein R9 and R10 are the same or different 'each of which is independently hydrogen or a trans group, R11 is hydrogen 't-butyl, carboxylic acid (_c〇〇H), methyl ester (-COOCH3), g The base (_c〇〇czH5) or the butyl group (_c〇〇C3H7). The photoresist peeling composition according to claim 8, wherein the anticorrosive agent is contained in an amount ranging from 0.01 to 5 wt% based on the total weight of the composition. 10. A method of stripping photoresist, the method comprising the steps of: U coating a photoresist on a conductive metal film or an insulating film formed on a substrate; 2) forming a photoresist on the substrate 3) The photoresist that forms the pattern is used as a "mask" to the film or the insulating film and the electric gold 21 201118511 4) Use as the patent application Fan Yuan 筮 π π target range 1 to 9 The photoresist stripping composition according to any one of the preceding claims, wherein the photoresist is peeled off. 11. A method of stripping photoresist, the method comprising the steps of: 1) applying a photoresist to an entire surface of a substrate; 2) forming a photoresist pattern on the substrate; 3) forming a conductive metal film Or an insulating film on the substrate on which the photoresist pattern is formed; and 4) peeling the light using the photoresist stripping composition according to any one of claims 1 to 9. Resistance. twenty two