TW201120587A - Resist stripper composition for forming copper-based wiring - Google Patents

Abstract

Disclosed is a resist stripper composition for forming copper-based wiring, which uses a compound containing sulfone and/or sulfine and/or an ester as the stripper and which can effectively prevent the corrosion of a conductive metal layer of copper or copper alloy wiring and an insulating layer of silicon oxide or silicon nitride which are disposed under the resist, even without the use of isopropanol as an intermediate cleaner, and also can cleanly remove the deteriorated and/or cured resist even at low temperature in a short period of time.

Description

201120587 VI. Description of the invention: The original [previous technique] = semi-conducting circuit or flat plate (4) is coated on the substrate, formed on the substrate, or on the whole layer of the metal layer, or oxidized stone or nitride Insulation line. Then, the photoresist pattern is formed and the conductive or enamel or insulating layer is wet- or dry-etched as a hood, so that (4) Wei Tu (4) is moved to the lower layer of the photoresist, and then the stripper composition is used to remove unnecessary layers. Light resistance. The photoresist removal process for the process of manufacturing a semiconductor device or a flat panel display should be able to strip the photoresist at a low temperature for a short period of time, and should prevent the photoresist from being on the substrate and should not damage the light. The metal layer or insulating layer of the barrier. The Cu-based metal layer including the Cu layer and the Cu_molybdenum layer was recently subjected to a metal layer for metal wiring in the field of semi-conducting or flat panel display. In the case of thin film transistors (TFT_LCDs), since resistance is a major factor in inducing RC signal delay, solving the Rc 仏唬 delay problem is the key to increasing panel size and achieving high resolution. ',,; and today's development of the use of amine compounds or diols - compounds as a stripper of the photoresist stripper composition because it severely corrodes the Cu-based metal layer, may cause environmental problems due to high toxicity, or in subsequent deposition Gate 3/16 201120587 The process of the pole insulation layer produces a higher defect rate and is not advantageous. It is therefore necessary to address this issue. SUMMARY OF THE INVENTION Accordingly, the present invention is intended to provide a photoresist stripper composition for forming a Cu-based wiring, which can effectively prevent an 'electrical metal layer, yttrium oxide or nitridation of Cu or 〇11 alloy wiring under the photoresist. The insulation of the crucible is corroded, even without the use of isopropyl alcohol. Group; ^This month is intended to provide a procedure for forming a photoresist stripper for Cu-based wiring, and Μ (4), early 0 and spray-type stripping species - Lu Hao cleanly remove g severely at low temperatures in a short period of time; Location = Relief and/or hardening of the photoresist with a wet residual treatment. The severely resistive peeling pattern provides a type of light for forming Cu-based wiring -= white which contains A) Β according to the total weight of the composition) 〇.〇κ5ί^ is a kind of additive including a compound of a compound, and a solvent of a compound represented by the following formula 4. ‘,余 «V% [Formula 2] 托托,% [Formula 3] Ο ～ 〇 〇 4/16 201120587 [Formula 4] Ο Ν I R9

Re In Formulas 1 to 4, Ri, R2, and independently are the alkane' and the core and R2, or & and 1 may be bonded to each other to form a C4~6 ring; r5 and ^ are each independently hydrogen, C1 ~4 alkyl, C1~4 alkyl, (10) alkoxy group, -R1(r(〇Ri))m_〇Rl, or -Rn-(〇^^ and ~ are each independently ^丨2 is hydrogen or C1~5 alkyl, and 尺5 and R6 can be bonded to each other 你6 you' and R7 is hydrogen or C1~5 alkyl, ^ and R9 are each independently hydrogen, C1~4 Base, or c 1~4 _ Sweep it;; ^ ϋ Α ^ ^ 4 acknowledgment, and R7#Rj are bonded to each other to C4~63⁄4, wherein the alkyl group is linear or branched alkyl. A method for manufacturing a semi-conducting «4 or flat plate using a micro-viewing method to form a semiconductor crucible, comprising using a photo-resistance according to the invention to remove (4) the photoresist. According to the present invention, The photoresist stripper composition can effectively prevent the conductive metal layer of the Cu or Cu alloy wiring under the photoresist, and the insulating layer etched with oxygen cut or nitrogen cut, even if isopropyl alcohol is not used as the intervening _. The photo-dissociating agent composition can be applied to all impregnation type, single-dip type And the health-type program, and can remove the photoresist which is degraded and/or hardened by the severe lithography treatment hot etching treatment at a low temperature in a short time. Therefore, the photoresist stripper composition according to the present invention is used. It is very useful to produce a semiconductor t-type or a flat panel display. 5/16 201120587 [Embodiment] The present invention relates to a photoresist stripper composition for forming a Cu-based wiring, which comprises A) 总 based on the total weight of the composition. ～45 wt% of one or more L compounds which are free of compounds represented by formulas 1 to 3, b) 〇.〇1 to 5 wt% of an additive comprising an azole compound, and (^ the remaining one is included by the following formula 4 a solvent representing the compound. [Formula 1]

[Formula 4]

In the formulas 1 to 4, 'R}, R2, , and the ruler 4 are independently Cl~6 and R4 can swim with each other. #_

Alkyl 'and R' and R2, or %' element group, C1~4 hydroxyalkyl group ~^io~f〇R,, W_r»r>

R5 and R6 are each independently hydrogen, an alkoxy group, -Ri3-(〇)n-(C=0)-(〇)〇.R]4, 201120587=base, and can be linked to each other&quot ; "Μ ^ base, heart and ~ each independently 虱, CJ~4 burning base, or C1~4 _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ In the present invention, the Cu-based wiring indicates a wiring formed of a CU layer or a CU alloy layer or a wiring of an H alloy layer in a semiconductor device. Including the Cu layer or Cu in the photoresist stripper composition according to the present invention, (4); the compound of the compound represented by the formulas 1 to 3 may be 1 to 45% by weight based on the composition of the composition I's preferably 3 〇~40% by weight of the amount used. : = the amount is in the above range, the ability to peel off the resistive photoresist 2 = and prevent the conduction of the cu layer or the like under the photoresist, and the designated examples of the compound represented by the formula 1 or 2 include the two: ethyl Sub-1, dimethyl sulfone, diethyl sulfone, and sulfolane, and designated examples of the compound represented by Formula 3 include dipropylene glycol, methyl propyl ketone, humiliation (tetra) acetic acid, gamma-butane, and n-butyl acetate. Ethyl lactate. For a long time GSg, and in the photo-ioning agent composition according to the present invention, the additive of the (8) compound is used to minimize the amount of impurities disposed under the photoresist and the insulating layer. Designated examples of wow compounds include 甲层二:, benzotriazine, like three bites, u, 4_三嗤, ::: sit, 'amino group · 4Η-ΐ52,4_three saliva, styrene benzene And three saliva, which = 2: f2H2 J, benzotriene *, benzotris- _ 5 · Lai, heterobenzotriene. Sit open - open two saliva_2_ base) _4,6_ two third butyl, and knee. The ticket, 7/J6 201120587, may be used alone or in combination of two or more thereof. Particularly useful is a triazole ring-containing compound. This is because the unshared electron pair of the nitrogen atom of the triazole ring is electrically bonded to Cu to inhibit metal corrosion. In the general case of using water but not using isopropyl alcohol as an intermediate cleaner for direct cleaning, the amine component of the photoresist stripper composition is mixed with water to form a highly corrosive alkaline hydroxyl ion, thereby promoting Cu*Cu. The metal layer of the alloy is rotted. However, (B) _ includes. The additive of the compound can form a complex with the gold in the test state, so that it can be immersed in the surface of the layer and the axial protective layer prevents the metal from being woven into the ion brain even if isopropyl alcohol is not used. The leaf is (:?=? The additive of the material is in accordance with the composition (4) ^ below the conductive gold: layer and the absolute;;: the photoresist can make the age feasible.,], and the potential benefit is in accordance with the invention The '(C) includes a solvent of the compound represented by the guanamine official represented by the formula 4' includes a compound of the formula 4. [Formula 4] Ο

= base, 8/16 201120587 A comparison of the amidoxime functional groups contained in (c) a solvent comprising a compound of no more than the other conventional solvents used to increase the solubility of the solvent by the polymer tree The ability of the compound city of the compound ^ The solvent of the compound to be represented by = 4 can be used to make the remaining amount of the total weight of the composition. In the case where the amount of the solvent is in the above range, it is excellent in terms of performance and resistance to electric current, and it is economically insignificant. A specified example of the compound represented by Formula 4 includes N-methyl. ^ Diketone, dimercaptoacetamide, dimethyl decylamine, N_decyl decylamine, B: amine, methyl acetate, group (2_ethyl) ethylamine, and 2 A diketone which may be used singly or in a mixture of two or more thereof. The photoresist stripper composition according to the present invention may further comprise (D) water. Ff>) Water may be a deionized water of 18 Μ Ω/cm or more suitable for a semiconductor program. The composition for forming a Cu-based wiring photoresist stripper according to the present invention can be applied to all impregnated, spray-type and monolithic films. Type stripping procedure. In addition, not only at high temperatures, but also at low temperatures and in a short period of time, the photoresist which is degraded and/or hardened by severe lithography and wet etching can be easily and cleanly removed. In addition, the corrosion of the conductive metal layer of the Cu or Cu alloy wiring disposed under the photoresist and the insulating layer of tantalum oxide or tantalum nitride can be minimized even when isopropyl alcohol is not used as the intermediate cleaner. Further, the present invention relates to a method of manufacturing a semiconductor device or a flat panel display using lithography to form a C11-type wiring, which comprises removing the photoresist after use using the photoresist stripper composition according to the present invention. The following description of the invention is intended to be illustrative and not restrictive Examples 1 to 13 and Comparative Examples 1 to 4: Preparation of a photoresist stripper composition 9/16 201120587 A composition for forming a Cu-based wiring photoresist stripper was prepared from the components shown in Table 1 below. Table 1 Dispersant Solvent Additive Type (% by weight) Species (% by weight) Species (% by weight) Species (% by weight) Example 1 Sulfolane 25 NMF 74.5 - - ΤΤΑ 0.5 Example 2 Sulfolane 35 ΝΜΡ 24.5 NMF 40 ΤΤΑ 0.5 Example 3 Sulfolane 40 DMAC 30 ΝΜΡ 29.5 Adenine 0.5 Example 4 DMSO 30 NMF 69 - - ΤΤΑ 1 Example 5 DMSO 35 ΝΜΡ 30 NMF 34 ΒΤΑ 1 Example 6 DMSO 40 DMAC 30 ΝΜΡ 29 Adenine 1 Example 7 DESO 35 NMF 63.5 - - ΤΤΑ 1.5 Example 8 DPGMEA 35 NMF 64.5 - - ΤΤΑ 0.5 Example 9 DPGMEA 35 ΝΜΡ 24.5 NMF 40 ΤΤΑ 0.5 Example 10 PGMEA 40 DMAC 30 ΝΜΡ 29.5 Adenine 0.5 Example 11 PGMEA 30 NMF 69 - - ΤΤΑ 1 Example 12 GBL 35 ΝΜΡ 30 NMF 34 ΒΤΑ 1 Example 13 GBL 40 DMAC 29 ΝΜΡ 30 Adenine 1 Comparative Example 1 DGA 15 NMF 84 - - ΤΤΑ 1 Comparative Example 2 ΜΕΑ 30 BDG 70 - - Comparative Example 3 DMEA 25 BDG 35 ΝΜΡ 40 - - Comparative Example 4 DMEA 25 BDG 35 ΝΜΡ 39 ΤΤΑ 1 DMSO: Dimercaptosulfoxide DESO·Diethyl sapphire DPGMEA: Dipropylene glycol oxime ether acetate PGMEA: Propylene glycol oxime ether acetate GBL: - Butyrolactone DMEA: Dimercaptoethanolamine oxime: Monoethanolamine DGA: Diethylene glycolamine oxime: Ν-decylpyrrolidone 10/16 201120587 BDG: Butanediol DMAC: Dimercaptoacetamide N-fluorenyl Indoleamine TTA: mercaptobenzotriazole BTA: 1,2,3_benzotriazole Test Example: Evaluation of the nature of the engraving property on the peeling performance and corrosion resistance of the Cu wiring Example 1 to η Comparative Example 1 The photoresist composition of ~4 was evaluated by the following method. And the program using the TFT circuit forming the LCD is in the glass. , the single metal layer of Ai's area is 3 denier / U layer. Then, a positive photoresist was applied and dried, and then the test was performed by performing Γ=Γ, thereby preparing a test sample. In the case of the tetravalent ~ _ 丨 ~ 4 fine _ 敝 维持 维持 维持 维持 维持 维持 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 New Zealand will cut the water for 6 seconds and dry with nitrogen. After the end of drying, FE_SEM was used to enlarge 40,00 (M〇, 〇〇〇 times and how many photoresists were observed to be peeled off from the test sample. The results are shown in Table 2 below. ° (2) Corrosion resistance 1 Examples 1 to 13 and The photoresist stripper compositions of Comparative Examples ~ 4 were maintained at 60 ° C, and the test samples prepared as described above were immersed therein for 3 minutes, washed with deionized water for 30 seconds, and then dried with nitrogen. After using FE-SEM to enlarge 40,000 to 8 〇, the degree of corrosion of the surface, lateral surface and cross section of the test sample was observed by doubling. The results are shown in the following Table 2. (3) Corrosion resistance 2 Examples 1 to 13 And compare your C and will maintain the photoresist stripper composition as described above and then take the test sample out of the sample in the filament for 10 minutes. The stripping procedure is carried out continuously - 7, 3 seconds and dried with nitrogen. Take this 40,000~8〇, 〇〇〇 而 and observe the second: then use the fe-SEM rose face to the extent of the rot. The results are shown in the ", heart surface, lateral surface and cross-cut ※ peeling performance Evaluation criteria ◎: Excellent I 〇: Good △: X: Bad ※ Evaluation of anti-sponsor rice performance The principle is that there is no corrosion on the surface and lateral surfaces of the CU layer, the underlying metal layer and the alloy layer, and the surface and lateral surfaces on the lateral surface and the lateral surface are: Cu: Cu layer, underlying metal layer and alloy rhinoceros slightly Corrosion 曰 A. Cu layer, underlying metal layer and alloy layer have partial corrosion day X. Cii layer, underlying metal layer and alloy layer have severe corrosion 12/16 201120587 Table 2 Example 1 ^i±^.(4〇 cC)

As is apparent from Table 2, the photoresist of Examples 1 to 13 is used as a release agent to improve the anti-aliasing effect when the photoresist is peeled off using ?:4 or a monol. (4) Excellent touch performance, and great light resistance (4), duck makes tenderness. This is good [Simple diagram description] None [Main component symbol description] None 13 / 16

Claims (1)

201120587 VII. Patent application scope: 1. A photoresist stripper composition for forming a cu-based wiring, which comprises, according to the total weight of the composition, A) 1 to 45 wt% of one or more selected from the following formulas: The compound of the compound 'B) 〇.〇1~5 by weight. / ❶ - an additive comprising an azole compound, and C) the remainder being a solvent comprising a compound of the following formula 4: [Formula 1] V Ri, R2 [Formula 2] 〇II R3'S'R4 [Formula 3] 0 Rs^O^6 [Formula 4] Ο Rs In the formulae I to 4, Ri, R2, R3 and R4 are each independently α?6 alkyl, and Ri and R2, or Rs and Re may be bonded to each other to form a C4~6 ring; Independently hydrogen, Cl~4 alkyl, C1-4 hydroxyalkyl, Cl~8 alkoxyalkyl, -Rl(r(0Rl))m_0Ri2, or -R]3-(0)n-(C =0)-(〇)〇-RI4 'where is the natural number from I to 4, n 14/16 201120587 and R14 are each independently 5 and the heart can be mutually 〇 or 1, 〇 is 〇 or 1, R1 (), Rn, R]3, C1~5 fluorenyl, R12 is hydrogen or Cl~5 alkyl, and joined to form a C4~6 ring; and 7 is 虱 or CI~5 院基' Rs and R9 are independently Is hydrogen, c 〜 4 alkyl, or C 1-4 hydroxyalkyl, and Rs can be bonded to each other to form a C 4 -6 ring ^ wherein the alkyl group is linear or branched alkyl., 2. 3. 4. The photoresist stripper composition of the patent application scope, wherein the compound represented by formulas ! to 3 is selected from the group consisting of dimethyl sulfoxide, diethyl hydrazine, dimethyl stone, diethyl hard, and ring. Top, dipropylene glycol methyl acetate, propylene glycol oxime ether acetate, γ-butyrolactone, n-butyl acetate, ethyl butyrate, and lactic acid The group consisting of ethyl esters, such as the photoresist stripper composition of claim 1, wherein the azole compound comprises - or a plurality of selected from the group consisting of methyl stupid and trisal, 1, 2, 3, stupid and triple saliva, 1,2,3- sit J,2,4·2 0 sit, 3-aminotrisal, 4-amino-4Η-1,2,4·three=, 1-yellow and triple m Triterpenoids, 2_曱丝和三. Sit, benzotriazole-5-carboxylic acid, nitro benzotriazole, 2-(2H-benzotriazol-2-yl) 4,6-one second A group consisting of butyl phenol and adenine. The photoresist stripper composition of claim 1 wherein the compound represented by formula 4 comprises one or more selected from the group consisting of N-fluorenyl. G, dimethyl acetamide, dimethyl decylamine, N-decyl decylamine, acetamidine, N-mercaptoacetamide, N-(2-hydroxyethyl) acetamide And a group consisting of 2_pyrrolidone. 5' The photoresist stripper composition according to claim 1 of the scope of the patent, further comprising water. 6. Photoresist stripping according to item i of claim patent The composition of the agent, which does not contain an amine compound. 15/16 201120587 (9) The removal of the square of the product of He Cai’s (4) The light-off agent composition of the first item: the species, the copper-based wiring is formed by lithography to produce a flat-panel display from /, including the use of the photoresist stripper composition as disclosed in claim 11 After the light resistance. 16/16 201120587 IV. Designated representative map: (1) The representative representative of the case is: (No). (2) A brief description of the symbol of the representative figure: »»», 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: [Formula 1] [Formula 2] 0 [Formula 3] 0 2/16