CN101373342B

CN101373342B - Acidic stripping liquid and preparing method thereof

Info

Publication number: CN101373342B
Application number: CN200810155128XA
Authority: CN
Inventors: 殷福华
Original assignee: Jiangyin Jianghua Microelectronic Material Co Ltd
Current assignee: Jiangyin Jianghua Microelectronic Material Co., Ltd.
Priority date: 2008-10-23
Filing date: 2008-10-23
Publication date: 2011-03-02
Anticipated expiration: 2028-10-23
Also published as: CN101373342A

Abstract

The invention relates to an acidic peeling liquid, which is prepared by synthesis after reaction of sulphuric acid and hydrogen dioxide used as raw materials., and is characterized in that ethylene diamine tetraacetic acid with concentration of 0.3-1.0 wt percent is contained in the prepared solution. The invention further relates to a method for preparing the acidity peeling liquid. The invention has the advantages that the stability of products is high, preserves the products for a long time, and is suitable for mass industrial production.

Description

A kind of acidic stripping liquid and preparation method thereof

One, technical field

The present invention relates to a kind of stripper, relate in particular to a kind of acidic stripping liquid and preparation method thereof.

Two, technical background

The light processing procedure that is used for integrated circuit technology and semiconductor technology removes dry method and removes photoresist/and crosslinked residue after the etching and the acidic stripping liquid of sidewall high molecular polymer are colourless transparent liquid, 290 ℃ of boiling points, density (20 ℃) is 1.82 ± 0.01g/ml, uses the product percent of pass and the quality that can effectively improve producer behind this product.At present acidic stripping liquid is that raw material reacts synthetic and makes with sulfuric acid and hydrogen peroxide; There is following shortcoming in this acidic stripping liquid: because the synthetic reaction of sulfuric acid and hydrogen peroxide is reversible reaction, and the acidic stripping liquid activity height, the poor stability that make, the holding time of its product is just short, makes the acidic stripping liquid can only now-making-now-using; Otherwise the acidic stripping liquid that makes is along with the growth of holding time, its effective constituent can reduce because of backward reaction, thereby effect is peeled off in influence, thereby the detachment rate of product is descended greatly and inhomogeneous, can't reach the effect of peeling off fully thus, thereby the production of producer is used in influence.

Three, technology contents

At above-mentioned shortcoming, the object of the present invention is to provide long acidic stripping liquid of a kind of good stability and holding time.

Technology contents of the present invention is, a kind of acidic stripping liquid, and it is that raw material reacts synthetic and makes by sulfuric acid and hydrogen peroxide; It is characterized in that containing in the solution that makes ethylenediamine tetraacetic acid (EDTA), its concentration is 0.3～1.0 weight %.

In above-mentioned acidic stripping liquid, peroxosulphuric concentration is 8.5～10.3 weight %, and sulfuric acid concentration is 85.0～95.0 weight %, concentration of hydrogen peroxide 0.5～1.0 weight %.

Another object of the present invention is to improve the preparation method of above-mentioned acidic stripping liquid.

Technology contents of the present invention is, a kind of preparation method of acidic stripping liquid, and it comprises the steps:

(1), adding concentration earlier in reactor is sulfuric acid and the EDTA of 98 weight %, the addition of EDTA is 0.08～0.12% of a sulfuric acid weight, under agitation slowly add the hydrogen peroxide that concentration is 31 weight %, and control temperature of reaction at 45～55 ℃, the hydrogen peroxide of its adding and the volume ratio of sulfuric acid are 1:3～5;

(2), add hydrogen peroxide and at normal temperatures temperature control, under agitation add 0.25～1.0% EDTA of sulfuric acid weight again, make it suppress backward reaction;

(3), the above-mentioned solution that makes is filtered through the filtrator of 0.5 μ m, particle diameter is greater than harmful particle of 0.5 μ m in the solution to remove, and acidic stripping liquid gets product.

The acidic stripping liquid that the present invention produces has added stabilizing agent EDTA on the basis of original technology, the principle of work of stabilizing agent: because metallic ion has the effect of catalytic decomposition to superoxide, the feasible peroxosulphuric instability that makes of minor metallic element in the product, after adding stabilizing agent EDTA, because EDTA energy complexing and separating metal ion, metallics can't directly be contacted with peroxosulphuric, thereby improve the stability of product, make it under the impregnable prerequisite of result of use, improve the degree of stability of product, make that product is the longest can be preserved 6 months, avoided this product now-making-now-using of former technology, this method can be applicable to large-scale production.

The present invention adopts in system peroxosulphuric processing procedure and adds stabilizing agent at twice, plays catalytic action for the first time, plays stabilization for the second time.

The advantage that the present invention is compared with prior art had is:

1, the stability of product is improved, and product can obtain preserving in the long period.

2, the effect of peeling off of product is not subjected to very big the influence after preserving the long period, and the present invention is suitable for large-scale industrial production.

Four, specific embodiment

The invention is further illustrated by the following examples, but be not limited to for embodiment.

Concentration is the sulfuric acid of 98 weight %, electron level, its index such as table 1

Classification	Electron level is in %
		Content (H ₂SO ₄)，％	97.0±1.0
Colourity (Hazen), max	10
		Ignition residue, max	5000
Chloride (Cl), max	200
		Nitrate (NO ₃)，max	200
Ammonium salt (NH ₄)，max	1000
		Reduction potassium permanganate material is (with SO ₂Meter), max	2000
Arsenic (As), max	10
		Copper (Cu), max	100
Iron (Fe), max	100
		Plumbous (Pb), max	100
Sodium (Na), max	500
		Particle 〉=1.0 μ m, max	25

Table 1

Concentration is the hydrogen peroxide of 31 weight %, electron level, its index such as table 2

Classification	Electron level is in %
		Content (H ₂O ₂)，％	31.0±1.0
Colourity (Hazen), max	10
		Free acid is (with H ⁺The mmol/100g meter), max	0.06
Evaporation residue, max	10000
		Chloride (Cl), max	500
Nitrogen compound (N), max	4000
		Phosphate (PO ₄)，max	2000
Sulfate (SO ₄)，max	2000
		Arsenic (As), max	50
Copper (Cu), max	20
		Iron (Fe), max	100
Plumbous (Pb), max	20
		Nickel (Ni), max	20
Sodium (Na), max	500
		Particle 〉=1.0 μ m, max	25

Table 2

EDTA, electron level, solid, its content 99.0%, Shanghai three little Industrial Co., Ltd.s produce.

In example 1, the sulfuric acid adding reactor, add EDTA150g, add the 20L hydrogen peroxide in cooling with under stirring, and control temperature of reaction below 50 ℃ with 80L content 98%; After adding, hydrogen peroxide is cooled to the EDTA that adds 400g under the normal temperature, stir after 20 minutes, the potpourri that the makes filtrator through 0.5 μ m is filtered, to remove in the potpourri particle diameter greater than harmful particle of 0.5 μ m, promptly get acidic stripping liquid, its EDTA concentration is 0.33 weight %.

In example 2, the sulfuric acid adding reactor, add EDTA150g, add the 20L hydrogen peroxide in cooling with under stirring, and control temperature of reaction below 50 ℃ with 80L content 98%; After adding, hydrogen peroxide is cooled to the EDTA that adds 550g under the normal temperature, stir after 20 minutes, the potpourri that the makes filtrator through 0.5 μ m is filtered, to remove in the potpourri particle diameter greater than harmful particle of 0.5 μ m, promptly get acidic stripping liquid, its EDTA concentration is 0.42 weight %.

In example 3, the sulfuric acid adding reactor, add EDTA150g, add the 20L hydrogen peroxide in cooling with under stirring, and control temperature of reaction below 50 ℃ with 80L content 98%; After adding, hydrogen peroxide is cooled to the EDTA that adds 1000g under the normal temperature, stir after 20 minutes, the potpourri that the makes filtrator through 0.5 μ m is filtered, to remove in the potpourri particle diameter greater than harmful particle of 0.5 μ m, promptly get acidic stripping liquid, its EDTA concentration is 0.68 weight %.

In example 4, the sulfuric acid adding reactor, add EDTA150g, add the 20L hydrogen peroxide in cooling with under stirring, and control temperature of reaction below 50 ℃ with 80L content 98%; After adding, hydrogen peroxide is cooled to the EDTA that adds 1400g under the normal temperature, stir after 20 minutes, the potpourri that the makes filtrator through 0.5 μ m is filtered, to remove in the potpourri particle diameter greater than harmful particle of 0.5 μ m, promptly get acidic stripping liquid, its EDTA concentration is EDTA concentration 0.92 weight %.

The physical index data such as the table 3 of example 1～4:

Claims

1. acidic stripping liquid, it is that raw material reacts synthetic and makes by sulfuric acid and hydrogen peroxide; It is characterized in that containing ethylenediamine tetraacetic acid in the solution that makes, its concentration is 0.3～1.0 weight %; Peroxosulphuric concentration is 8.5～10.3 weight % in the acidic stripping liquid, and sulfuric acid concentration is 85.0～95.0 weight %, concentration of hydrogen peroxide 0.5～1.0 weight %.

2. the preparation method of acidic stripping liquid according to claim 1, it comprises the steps:

(1), adding concentration earlier in reactor is sulfuric acid and the EDTA of 98 weight %, the addition of EDTA is 0.08～0.12% of a sulfuric acid weight, under agitation slowly add the hydrogen peroxide that concentration is 31 weight %, and control temperature of reaction at 45～55 ℃, the hydrogen peroxide of its adding and the volume ratio of sulfuric acid are 1: 3～5;