CN101178548B

CN101178548B - Alkaline-based developer composition

Info

Publication number: CN101178548B
Application number: CN2006101382511A
Authority: CN
Inventors: 郭光埌; 戴伟仁
Original assignee: NEW APPLIED MATERIALS CO Ltd
Current assignee: NEW APPLIED MATERIALS CO Ltd
Priority date: 2006-11-08
Filing date: 2006-11-08
Publication date: 2011-08-10
Anticipated expiration: 2026-11-08
Also published as: CN101178548A

Abstract

The invention relates to an alkali developer used for the image forming of photonasty resin after being exposed to UV, which comprises (A) pure water,(B) at least one alkali compound,(C) a defoamer the content of which is less than 500ppm, and(D) at least one nonionic interface activating agent the total content of which is 0.05 to 10 percent, wherein, the structural formula of the nonionic interface activating agent is characterized in that R1 is -H or -CH3; EO is polyoxyethylene; PO is polyoxypropylene; m and n can not be zero at the same time; m plus n is smaller than 25; and R2 is hydrophobic group.

Description

Alkaline-based developer composition

Technical field

The relevant a kind of developer solution component of the present invention refers to a kind of alkaline-based developer composition that the sensing optical activity resin forms ultraviolet (UV) exposure back image that is applied in especially.

Background technology

For making used minute circuit pattern in SIC (semiconductor integrated circuit) or LCD (LCD) circuit, on insulator layer on the substrate or conductive metal layer, evenly cover or apply a kind of fluoropolymer resin that comprises, the photoresistance composition of Photoactive compounds and solvent, the substrate that covers or apply bakes with evaporating solvent through temperature, the substrate that temperature baked selectively is exposed to the radiation such as the ultraviolet ray of some pattern, electronics or X ray, the substrate that exposed to the open air is roasting through heat again, bake substrate through developing pattern that generation is expected with after heat, the substrate that develops removes insulator layer or conductive metal layer with etching again, and removes remaining photoresist layer and transfer on substrate surface to finish micro pattern.

Moreover, after the sensing optical activity resin combination is filmed, bakes in advance, is exposed in process, remove unexposed filming partly though can use alkaline-based developer to dissolve, but also may be difficult to form photoresist image accurately after causing developing because of the do not develop remaining phenomenon of position particle (or not dissolved particles) of easy generation when developing; Especially, in the middle of more advanced LCD (LCD) circuit manufacture procedure,, will be enough to have a strong impact on the quality of product if the residue of generation or the residual phenomenon of metallic ion are arranged.

In the middle of existing technical field, Japanese kokai publication hei 10-10749 patent documentation, though disclose a kind of developer solution component that comprises that water, alkali compounds, teepol are formed, to obtain no residue, the preferable effect of video picture, yet when practical application, the defoaming that this known developer solution component showed, operating temperature, and chromatic photoresist dispersion stability is neither as expection is desirable, can't be fully in response to the diversified development of chromatic photoresist.

Summary of the invention

In view of this, fundamental purpose of the present invention promptly provide that a kind of development is good, defoaming is strong, allow operability temperature height, and take into account the dispersion stability of chromatic photoresist and the alkaline-based developer composition of avoiding residue to leave over, use in response to the chromatic photoresist variation, have the developing property that to adjust applicability.

Alkaline-based developer composition of the present invention includes (A) pure water, (B) at least a alkali compounds, (C) content less than the defoamer of 500ppm, the non-ionic surfactant of (D) at least a total content 0.05～10%; Wherein, the structural formula of non-ionic surfactant is:

It focuses on: the R1 in the middle of the structural formula of non-ionic surfactant be hydrogen (H) or methane (CH3); EO is oxirane (polyoxyethylene); PO is epoxypropane (polyoxypropylene), m and n not can be zero simultaneously, m+n is less than 25, R2 is a hydrophobic group; This hydrophobic group can be selected from: and phenyl, alkyl biphenyl class, naphthenic and lopps and cycloalkenyl group, wherein arbitrary or combination in any collocation.

Embodiment

For making your auditor know major technique content of the present invention, and embodiment, cooperate graphic being described as follows now:

Alkaline-based developer composition of the present invention is a kind of alkaline-based developer that is applied to the sensing optical activity resin to the formation of ultraviolet (UV) exposed images, and its its constituent includes:

(A) pure water mainly as the dispersion medium of developer solution, because water itself does not have toxicity and incendivity, therefore uses pure water not only with low cost as the dispersion medium of developer solution, and former material itself is easier to management, and the processing of waste liquid is also comparatively easy.

(B) at least a alkali compounds is mainly used in the resin that dissolves non-image part, and it can be selected from: (1) alkaline metal, alkaline earth metal hydroxide; (2) alkaline metal, alkaline earth metal carbonate and supercarbonate; Or (3) organic ammonium class:

In the middle of the structural formula of above-mentioned organic ammonium class, R1～R3 can be hydrogen (H), alkyl (hydrocarbon), hydrocarbon alkyl (hydroxyalkyl), and wherein at least one is the hydrocarbon alkyl.

(C) content is less than the defoamer of 500ppm, and in order to change the defoaming of the developer solution that looses, it can be for there not being siliceous non-ionic interfacial agent.

(D) non-ionic surfactant of at least a total content 0.05～10%; Wherein, the structural formula of non-ionic surfactant is:

In the middle of the structural formula of above-mentioned non-ionic surfactant, R1 be hydrogen (H) or methane (CH3); EO is oxirane (polyoxyethylene); PO is epoxypropane (polyoxypropylene), m and n not can be zero simultaneously, m+n is less than 25, R2 is a hydrophobic group, wherein the HLB value of hydrophobic group is controlled at 9～16; (HLB=7+11.7log (Mw/Mo), optimum value 10～14, Mo: the molecular weight of expression lipophilic group; Mw: the molecular weight of expression hydrophilic group.

When implementing, hydrophobic group can be selected from:

(1) the also phenyl of structural formula (a) can be two or more and phenyl;

R1～R7 in the middle of the structural formula (a) can be hydrogen atom (H), alkyl (Alkyl), aryl (Aryl), aralkyl (aralkyl).

(2) the alkyl biphenyl class of structural formula (b);

R1 in the middle of the structural formula (b) can be hydrogen atom (H) or alkyl (Alkyl).

(3) naphthenic (cyclic-alkane) of structural formula (c);

R1～R3 in the middle of the structural formula (c) can be hydrogen atom (H), alkyl (Alkyl), aryl (Aryl), aralkyl (aralkyl), naphthenic base (cyclic-alkane); R3 can be in arbitrary position of ring.

(4) the also lopps of structural formula (d) can be two or more and lopps;

R1～R6 in the middle of the structural formula (d) can be hydrogen atom (H), alkyl (Alkyl), aryl (Aryl), aralkyl (aralkyl), naphthenic base (cyclic-alkane).

(5) the also cycloalkenyl group of structural formula (e) can be two or more and cycloalkenyl group;

R1～R6 in the middle of the structural formula (e) can be hydrogen atom (H), alkyl (Alkyl), aryl (Aryl), aralkyl (aralkyl), naphthenic base (cyclic-alkane).

As shown in table 1, (characteristic of D01～D09 and K101～K105) and existing alkaline development fluid samples (D10 and K106) relatively for the alkaline development fluid samples that utilizes basic composition thing of the present invention to be modulated into according to the different formulations ratio;

In the middle of table 1, (Tetramethyl ammonium Hydroxide TMAH), is a kind of organic base to Tetramethylammonium hydroxide; Each sample of filling a prescription adds defoamer (non-ionic interfacial agent) 100～100PPM at last again; By the result of table one as can be known, use in the middle of the sample of Tetramethylammonium hydroxide, have characteristics such as development effect is preferable, residual less, good, the residual film of defoaming is few fully with sample D03, D04, D05; Use in the middle of the sample of potassium hydroxide, have characteristics such as development effect is preferable, residual less, good, the residual film of defoaming is few fully with sample K103, K104, K105; Confirm that the present invention can provide that a kind of development is good, defoaming strong, allow operability temperature height, and take into account the dispersion stability of chromatic photoresist and the alkaline-based developer composition of avoiding residue to leave over, use in response to the chromatic photoresist variation, have the developing property that to adjust applicability.

As mentioned above, the invention provides a kind of preferable feasible alkaline-based developer composition, the application of patent of invention is offered in the whence in accordance with the law; Yet, above implementation and graphic shown in, preferred embodiment of the present invention is not to limit to the present invention with this, be with, approximate with structure of the present invention, device, feature etc., identical such as, all should belong to of the present invention founding within purpose and the claim.

Claims

1. alkaline-based developer composition, its constituent include pure water, at least a alkali compounds, content and are used to improve the defoaming of developer solution, the non-ionic surfactant of at least a total content 0.05～10% less than the defoamer of 500ppm;

Wherein this alkali compounds is selected from the following group that constitutes: alkali metal hydroxide, alkaline earth metal hydroxide and structural formula are:

The organic ammonium class, R wherein ₁～R ₃Be hydrogen, alkyl, hydroxyalkyl, and wherein at least one is a hydroxyalkyl;

Wherein the structural formula of this non-ionic surfactant is:

Wherein:

R in the middle of the structural formula of this non-ionic surfactant ₁Be hydrogen or methyl; EO is an ethylene oxide unit; PO is a propylene oxide unit, and m and n can not be zero simultaneously, m+n is less than 25, R ₂Be hydrophobic group, wherein the HLB value of hydrophobic group is controlled at 9～16, HLB=7+11.7log (M _W/ M _O), M wherein _OThe molecular weight of expression lipophilic group, M _WThe molecular weight of expression hydrophilic group; This hydrophobic group is to be selected from the following group that constitutes:

(A) have the alkyl biphenyl class of following formula (b):

R wherein ₁Be hydrogen atom or alkyl;

(B) have the naphthenic of following formula (c):

R wherein ₁～R ₃Be hydrogen atom, alkyl, aryl, aralkyl, naphthenic base; R ₃Arbitrary position at ring;

(C) that have a following formula (d) and lopps:

R wherein ₁～R ₆Be hydrogen atom, alkyl, aryl, aralkyl, naphthenic base; And

(D) that have a following formula (e) and cycloalkenyl group:

R wherein ₁～R ₆Be hydrogen atom, alkyl, aryl, aralkyl, naphthenic base.