阅读说明：本技术 抗蚀剂剥离液组合物 (Resist stripping liquid composition ) 是由 久保贤一 谢双林 于 2021-09-17 设计创作，主要内容包括：本发明属于膜的表面处理技术领域,具体涉及一种抗蚀剂剥离液组合物,用于在半导体元件、液晶面板元件等的制造中的膜的表面处理。本发明抗蚀剂剥离液组合物包括：(A)抗蚀剂剥离溶液,选自碳酸亚乙酯,碳酸亚丙酯,γ-丁内酯,环戊酮和碳酸甘油酯中的一种或多种；(B)在分子中具有氧化烯基的表面活性剂；(C)在分子中具有乙氧基,丁氧基或这两个取代基两者的基于乙二醇醚的有机化合物。本发明提供在充分利用含有氧化烯系表面活性剂的抗蚀剂剥离液的特性的同时,溶解了作为氧化烯系表面活性剂的分解产物的1-十六烷醇等水不溶性微粒,在基板表面上防止重新附着的抗蚀剂剥离液组合物。该组合物对在基板表面上形成的金属布线的腐蚀性极低。(The present invention belongs to the technical field of film surface treatment, and particularly relates to a resist stripping liquid composition for surface treatment of films in the manufacture of semiconductor elements, liquid crystal panel elements, and the like. The resist stripping liquid composition of the invention comprises: (A) a resist stripping solution selected from one or more of ethylene carbonate, propylene carbonate, γ -butyrolactone, cyclopentanone, and glycerol carbonate; (B) a surfactant having an oxyalkylene group in a molecule; (C) glycol ether-based organic compounds having ethoxy groups, butoxy groups, or both substituents in the molecule. The present invention provides a resist stripping liquid composition which can dissolve water-insoluble particles such as 1-hexadecanol which is a decomposition product of an oxyalkylene surfactant while making full use of the characteristics of a resist stripping liquid containing the oxyalkylene surfactant, and prevent re-adhesion on the surface of a substrate. The composition has extremely low corrosiveness to metal wiring formed on the surface of a substrate.)

1. A resist stripping liquid composition, comprising:

(A) 100 parts by mass of a resist stripping solution selected from one or more of ethylene carbonate, propylene carbonate, γ -butyrolactone, cyclopentanone, and glycerol carbonate;

(B) 0.01 to 10 parts by mass of a surfactant having an oxyalkylene group in a molecule;

(C) 1 to 40 parts by mass of an organic glycol ether-based compound having an ethoxy group, a butoxy group or both of these substituents in the molecule.

2. The resist stripping liquid composition according to claim 1, characterized in that the glycol ether organic compound of component (C) is an organic compound having a linear structure.

3. The resist stripping liquid composition according to claim 2, characterized in that the (C) component glycol ether type organic compound is an organic compound having a branched structure selected from linear structures.

4. The resist stripping liquid composition according to claim 1, characterized in that the glycol ether organic compound of component (C) is an organic compound having 2 to 12 carbon atoms.

5. The resist stripping liquid composition according to any one of claims 1 to 4, characterized in that the (C) component glycol ether organic compound is freely mixed with water.

6. The resist stripping liquid composition according to claim 5, characterized in that the component (C) glycol ether organic compound is prepared by mixing 50 wt% or more of glycol ether organic compound and 100 wt% of water based on water, and 1 wt% of higher saturated aliphatic alcohol having a molar mass of 250g/mol or less is dissolved therein, and is insoluble in water.

7. The resist stripping liquid composition according to claim 6, wherein the content of the (C) component glycol ether-based organic compound is 1 to 40 wt% with respect to the total amount of the resist stripping solution.

8. The resist stripping liquid composition according to claim 1, characterized in that the (a) component resist stripping solution is made of one or more of (a1) ethylene carbonate and (a2) propylene carbonate, γ -butyrolactone, cyclopentanone and glycerol carbonate.

9. The resist stripping liquid composition according to claim 8, characterized in that, relative to the total amount of the (A) component resist stripping liquid, (A1) ethylene carbonate is 20 wt% to 80 wt%; 20 to 80 weight percent of gamma-butyrolactone; (A2) the propylene carbonate accounts for 20-80 wt%; the glycerol carbonate accounts for 0 to 50 weight percent.

10. The resist stripping liquid composition according to claim 9, characterized by comprising 50 to 70 wt% of the ethylene carbonate, 30 to 50 wt% of the gamma-butyrolactone, and 0 to 30 wt% of the glycerol carbonate, relative to the total amount of the (a) component resist stripping liquid.

11. The resist stripping liquid composition according to claim 1, characterized in that the content of γ -butyrolactone is 60 to 99 wt% with respect to the total amount of (a) component resist stripping liquid.

12. The resist stripper composition according to claim 1, wherein the content of the propylene carbonate is 60 to 99 wt% with respect to the total amount of the (a) resist stripper.

13. The resist stripping liquid composition according to claim 1, characterized in that the (B) component oxyalkylene surfactant is a nonionic surfactant.

14. The resist stripping liquid composition according to claim 1, characterized in that the oxyalkylene surfactant of component (B) is a surfactant having an oxyethylene group and having 10 to 500 carbon atoms.

15. The resist stripping liquid composition according to claim 1, characterized in that the oxyalkylene surfactant of component (B) is a surfactant having oxyethylene groups and oxypropylene groups and having 10 to 500 carbon atoms.

16. The resist stripping liquid composition according to claim 1, characterized in that the amount of oxyethylene groups and oxypropylene groups contained in the oxyalkylene surfactant of component (B) is 6 or less in terms of the ratio of the amount represented by oxypropylene group/oxyethylene group.

17. The resist stripping liquid composition according to claim 1, characterized in that the molar ratio of the oxyethylene group contained in the oxyalkylene surfactant of component (B) to the oxypropylene group is set in the molar ratio of oxyethylene group: 0.2 in terms of oxypropylene group: 1 or more and 3: 1 or less.

18. The resist stripping liquid composition according to claim 1, characterized in that it contains 30 parts by mass or less of water per 100 parts by mass of the entire resist stripping liquid composition.

19. The resist stripper composition according to claim 1, wherein the resist stripper composition is used for stripping novolak resin type positive resists.

Technical Field

The present invention belongs to the technical field of film surface treatment, and particularly relates to a resist stripping liquid composition for surface treatment of films in the manufacture of semiconductor elements, liquid crystal panel elements, and the like.

Background

In the manufacture of semiconductor devices, liquid crystal panel devices, and the like, a silicon semiconductor layer, a gate insulating film such as a silicon oxide film, an electrode film such as an indium tin oxide film (ITO film), a protective insulating film such as a silicon nitride film, and the like are formed on a substrate such as a silicon wafer, glass, or the like by vacuum deposition or chemical vapor deposition. Then, a photoresist is uniformly applied on the gate insulating film or the protective insulating film, and then the photoresist is selectively exposed to light and developed to form a photoresist pattern. Then, the gate insulating film or the protective insulating film is selectively etched using the pattern as a mask to form a fine circuit, and then an unnecessary photoresist layer is removed with a resist stripping liquid to produce a liquid crystal panel element.

Conventionally, as a resist film stripping solution made of a novolak resin, an amine-based resist stripping solution obtained by adding a water-soluble organic solvent such as dimethyl sulfoxide (DMSO) and water to an amine-based compound such as Monoethanolamine (MEA), N-methylaminoethanol, N-methyl-2-pyrrolidone, or the like has been used.

As a resist stripping liquid other than amine-based ones, there are known: an etching resist removing liquid containing an etching resist having reducibility and adsorptivity, a water-soluble organic solvent, water and a surfactant, for example, Japanese patent laid-open No. 2008-58624. In the process of forming the photoresist pattern, a rinsing step of removing the resist stripping liquid adhering to the substrate by washing with pure water is performed after the resist stripping step after etching. When a resist stripping liquid other than amine is used, the rinsing step with pure water has the following problems: the resist stripper dissolved in the resist stripper precipitates on the substrate surface, or fine particles of the resist stripper dispersed in the resist stripper reattach to the substrate surface, thereby generating resist residue.

In order to prevent the above-mentioned dissolution of the resist stripper on the substrate surface or the reattachment of the particles of the resist stripper on the substrate surface, it is known to use a rinsing liquid containing a surfactant in pure water in the rinsing step, for example, japanese patent laid-open No. 2006-11054. Further, international patent No. WO2014002151a1 proposes a resist stripping solution in which glycerol carbonate is added to at least one selected from the group consisting of ethylene carbonate, propylene carbonate, γ -butyrolactone and cyclopentanone.

However, when the rinse liquid contains a surfactant, the following problems arise: an additional rinsing step of washing the rinsing liquid becomes necessary, and maintenance cost of the washing equipment is incurred by the rinsing liquid bubbles.

International patent WO2018/020837a1 discloses a resist stripper composition containing a surfactant having an oxyalkylene group. When the photoresist layer is removed with the resist stripping solution, the solution temperature is generally 40 ℃ or higher, and the photoresist layer is reused. However, known oxyalkylene-based surfactants decompose at temperatures above 40 ℃, and the decomposition product of the oxyalkylene-based surfactant is water-insoluble fine particles such as n-hexadecanol (n-HDA), which are combined with the decomposition product of the photoresist and reattach to the substrate surface to form a resist residue. Therefore, the resist stripping solution containing the oxyalkylene-based surfactant cannot be reused by raising the temperature, and requires frequent liquid exchange, which causes a problem of an increase in environmental load.

Disclosure of Invention

The present invention provides a resist stripping liquid composition technology which can dissolve water insoluble particles such as 1-hexadecanol which is a decomposition product of an oxyalkylene surfactant and prevent re-adhesion on a substrate surface while fully utilizing the characteristics of a resist stripping liquid containing the oxyalkylene surfactant.

Another object of the present invention is to provide a resist stripping solution composition technology that can be repeatedly used in the resist stripping solution.

Further, an object of the present invention is to provide a resist stripping solution composition technology which is extremely low in corrosiveness to a metal wiring formed on a substrate surface.

In order to achieve the purpose, the technical scheme of the invention is as follows:

a resist stripping liquid composition comprising:

(A) 100 parts by mass of a resist stripping solution, one or more selected from the group consisting of ethylene carbonate, propylene carbonate, γ -butyrolactone, cyclopentanone, and glycerol carbonate;

(B) 0.01 to 10 parts by mass of a surfactant having an oxyalkylene group in a molecule;

(C) 1 to 40 parts by mass of an organic glycol ether-based compound having an ethoxy group, a butoxy group or both of these substituents in the molecule.

In the resist stripping solution composition of the present invention, component (a) plays a role in stripping a resist film formed on a substrate surface from the substrate, and component (a) is a resist stripping solution containing a compound having a ring structure composed of carbon and oxygen.

The component (B) in the present invention can suppress the generation of resist residue in the pure water rinsing step after the resist stripping, and the oxyalkylene surfactant used as the component (B) preferably has an oxyethylene group (EO) as a hydrophilic group or an oxypropylene group (PO) as a hydrophobic group in addition to the oxyethylene group (EO).

The component (C) in the present invention dissolves a decomposition product resulting from thermal decomposition of the component (B) and combines with a product of resist stripping to suppress formation of resist residue in the pure water rinsing step after resist stripping.

Preferably, the (C) component glycol ether-based organic compound is an organic compound having a linear structure.

Further, the (C) component glycol ether type organic compound is an organic compound having a branched structure selected from a linear structure.

Preferably, the glycol ether organic compound of the component (C) is an organic compound having 2 or more and 12 or less carbon atoms.

Preferably, the (C) component glycol ether-based organic compound is freely mixed with water.

Preferably, the glycol ether organic compound of component (C) is prepared by dissolving 1 wt% of a higher saturated aliphatic alcohol having a molar mass of 250g/mol or less in an aqueous solution of a glycol ether organic compound in an amount of 50 wt% or more and 100 wt% of water, based on water, and is insoluble in water.

Preferably, the content of the (C) component glycol ether-based organic compound is 1 to 40 wt% with respect to the total amount of the resist stripping solution.

Preferably, the (a) component resist stripping solution is made of one or more of (a1) ethylene carbonate and (a2) propylene carbonate, γ -butyrolactone, cyclopentanone, and glycerol carbonate.

Further, the ethylene carbonate (A1) is 20 to 80 wt% with respect to the total amount of the resist stripping liquid (A).

Further, the gamma-butyrolactone accounts for 20 wt% -80 wt%.

Further, the propylene carbonate (A2) is 20 wt% to 80 wt%.

Further, the content of the glycerol carbonate is 0 to 50 wt%.

Preferably, the component (A) resist stripper contains 50 wt% to 70 wt% of the ethylene carbonate, 30 wt% to 50 wt% of the gamma-butyrolactone, and 0 wt% to 30 wt% of the glycerol carbonate, relative to the total amount of the component (A) resist stripper.

Preferably, the content of gamma-butyrolactone is 60 to 99 wt% relative to the total amount of (a) component resist stripping liquid.

Preferably, the content of the propylene carbonate is 60 to 99 wt% with respect to the total amount of the (a) resist stripper.

Preferably, the (B) component oxyalkylene surfactant is a nonionic surfactant.

Preferably, the (B) component oxyalkylene surfactant is a surfactant having an oxyethylene group and having a carbon number of 10 or more and 500 or less.

Preferably, the (B) component oxyalkylene surfactant is a surfactant having an oxyethylene group and an oxypropylene group and having a carbon number of 10 or more and 500 or less.

Preferably, the amount of oxyethylene groups and oxypropylene groups contained in the (B) component oxyalkylene surfactant is 6 or less in terms of the ratio of the amount represented by oxypropylene group/oxyethylene group.

Preferably, (B) component the molar ratio of oxyethylene groups to oxypropylene groups contained in the oxyalkylene surfactant, is such that the ratio of oxyethylene groups: 0.2 in terms of oxypropylene group: 1 or more and 3: 1 or less.

Preferably, the resist stripping liquid composition contains 30 parts by mass or less of water per 100 parts by mass of the entire composition.

Preferably, the resist stripper composition is used for stripping novolak resin type positive resists.

By adopting the scheme, the resist stripping solution disclosed by the invention has excellent stripping performance. Further, even if the resist is peeled and then directly rinsed with pure water, the material from which the resist is peeled does not precipitate on the substrate surface and does not re-adhere. Further, since the composition of the component dissolves the thermal decomposition product of the oxyalkylene-based surfactant contained in the resist stripping solution, the resist stripping solution can be heated to strip the resist film and reused. Further, there is little corrosion action on the substrate surface of the copper wiring and the aluminum wiring.

Drawings

FIG. 1 is an optical micrograph showing a state in which no resist-peeled matter is deposited or adhered on a substrate according to an embodiment of the present invention;

FIG. 2 is an optical micrograph showing a state in which a resist-peeled substance is deposited or adhered on a substrate of a comparative example;

FIG. 3A is a plan view schematically showing a sample used in the example of the present invention;

fig. 3B is a side view schematically showing the sample shown in fig. 3A.

Detailed Description

The invention is further described below with reference to the following figures and specific examples.

In the following examples, the abbreviations each represent the following substances or groups.

EC: ethylene carbonate;

PC: propylene carbonate;

GBL: gamma-butyrolactone;

and (3) CP: cyclopentanone;

GC: glycerol carbonate;

MEA: monoethanolamine;

DMSO, DMSO: dimethyl sulfoxide;

BDG: diethylene glycol monobutyl ether;

EO: oxyethylene (-O-CH2CH 2-);

i-PO: oxidized isopropenyl (-O-C (CH3) H-CH 2-);

PO: oxidized isopropenyl (-O-C (CH3) H-CH2-) or oxidized n-propenyl (-O-CH2-CH2-CH 2-);

BG: 2-butoxyethanol;

iBDG: 2-2 isobutoxyethoxyethanol;

EtOH: ethanol;

CaHb-O- (EO) p- (PO) q-H: a polyoxyalkylene alkyl ether having a polyoxyalkylene group as a main chain,

wherein a is 22, b is 45, p is 20, q is 0

The product name is as follows: NIKKOL BB-20 (molecular weight 1206).

TABLE 1

Evaluation of resist stripping solution reattachment resist decomposition product

Simulation experiment (evaluation of reattachment of resist decomposition product by resist remover)

Evaluation of resist stripping using a sample (resist stripper) adjusted at the mixing ratio shown in table 1 in the evaluation of resist stripping, as shown in the optical micrograph shown in fig. 1, the mixing ratio at which no precipitate or deposit was formed was measured on the surface of the substrate after rinsing. An optical micrograph in the case of precipitate or deposit formation is shown in fig. 2. FIG. 3A is a plan view schematically showing a sample used in an embodiment of the present invention; fig. 3B is a side view schematically showing the sample shown in fig. 3A. In the mark, 1: a glass substrate; 2: a nitride film; 3: aluminum film; 4: and (4) resist.

TABLE 1 (continuation)

Evaluation of resist stripping solution used for Long period

Simulation experiment (evaluation of Long-term use by heating resist stripper)

The samples (resist stripping solutions) adjusted in the mixing ratios shown in Table 2 were heated to 60 ℃ with a thermal stirrer, and stored in a thermostatic bath at 60 ℃ for 1 to 30 days at a constant temperature. On the surface of the glass substrate with the nitride film, the presence or absence of the heat-induced decomposition product of the resist stripping liquid composition component to be evaluated was evaluated.

(1.1) evaluation of Long-term use of heated resist stripping solution

The samples (resist stripping solutions) adjusted in the mixing ratios shown in Table 2 were heated to 60 ℃ with a thermal stirrer, and stored in a thermostatic bath at 60 ℃ for 1 to 30 days at a constant temperature.

30 mass% of each resist stripping solution was added to 100 mass% of water at room temperature, and stirred with a stirrer for 10 minutes. The supernatant was collected by a 1% mass dropper, and a sample was dropped onto the surface of a borosilicate glass substrate having a nitride film of 2cm in length, 2cm in width and 0.7cm in thickness, dried by a nitrogen air gun, and observed for fine particles by an optical microscope.

(1.2) evaluation

Evaluation of resist stripping liquid used for a long period:

no decomposition product adhered to the substrate surface

X having decomposition products adhered to the surface of the substrate

TABLE 2

Evaluation of resist stripping Rate

The resist stripping speed of the sample (resist stripping solution) adjusted by the mixing ratio in table 3 was evaluated as follows.

Which is an evaluation of the reattachment of resist decomposition products by the resist stripping solution.

After the same resist was applied to the same glass substrate surface, baking was performed at 110 ℃ and 130 ℃ to form a resist film having a thickness of 2 μm. The obtained glass substrate with the resist film was immersed in 50g (room temperature) of the resist stripping liquid composition of each example for a predetermined time in the range of 6 to 12 seconds, and shaken once/second. Then, as in "evaluation of reattachment of the decomposition product of the resist by the resist stripping solution", the surface was immersed in pure water overflowed in a vessel and dried with nitrogen gas, and then the surface was observed with the same optical microscope as described above. The results in Table 3 show that no decomposition product was adhered to the substrate surface.

Evaluation of

Evaluation of resist stripping liquid used for a long period:

no decomposition product adhered to the substrate surface

X having decomposition products adhered to the surface of the substrate

TABLE 3

Evaluation of corrosion of metal wiring

The corrosion properties of the resist stripping liquid compositions shown in table 4 on metal wiring were evaluated as follows. Similar to the above "evaluation of reattachment of decomposition products of the resist by the resist stripping liquid", a simulated metal wiring board was prepared by sputtering Cu, Al and Mo onto a glass substrate the simulated metal wiring board was immersed in 200g of the resist stripping liquid composition to be evaluated, and heated to 60 to 80 ℃ for 100 minutes with stirring. After the immersion, the amount of metal elution in the resist stripper composition was measured by ICP-MS (inductively coupled plasma mass spectrometer), and from the result, the etching rates of Cu, Al and Mo per minute were determined. The results are shown in Table 4.

TABLE 4

As is clear from table 4, the resist stripping liquid of the present invention can suppress corrosion of metal wiring, as compared with the amine-based resist stripping liquid.

The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.