Etching agent, etching method and etching agent preparation liquid

An etchant and aqueous solution technology, which is applied in the field of etchant for titanium-based metals, can solve the problems of shortened solution life and high copper leaching, and achieve the effects of stable etching rate, prolonging solution life, and inhibiting decomposition

Active Publication Date: 2016-03-02
FUJIFILM CORP
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0018] However, when these etchants are used for a semiconductor substrate having a titanium-based metal and metallic copper or a copper alloy having a large volume relative to the titanium-based metal, since the metallic copper or copper alloy has a large volume compared to titanium, it has been used. It is known that there are problems in that the amount of copper (copper oxide) eluted from metallic copper or copper alloy is too large, the eluted copper (copper oxide) causes decomposition of hydrogen peroxide, the life of the solution is shortened, or the etchant needs to be properly controlled. The concentration of hydrogen peroxide in; etc.

Method used

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  • Etching agent, etching method and etching agent preparation liquid
  • Etching agent, etching method and etching agent preparation liquid
  • Etching agent, etching method and etching agent preparation liquid

Examples

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preparation example Construction

[0080] As long as the preparation method of the etchant of the present invention is capable of preparing (A) hydrogen peroxide, (B) a phosphonic acid chelating agent having a nitrogen atom in the structure, (C) an alkali metal hydroxide and (D) having at least 1 Hydroxyl and at least 3 carboxyl organic acids, and (E) pH regulators and (F) aqueous solutions of surfactants used as needed, the preparation method itself is not particularly limited. Specific examples of the preparation method include, for example, the following method: adding (B) a phosphonic acid-based chelating agent having a nitrogen atom in the structure, (C) an alkali metal hydroxide, and (D) having After the organic acid having at least 1 hydroxyl group and at least 3 carboxyl groups, if necessary, add (F) surfactant, and further add (E) pH adjuster to adjust pH if necessary, and then stir to form a uniform aqueous solution. The etchant of the present invention thus prepared may be subjected to filtration tre...

Embodiment 1

[0116] Embodiment 1 Preparation-1 of etchant of the present invention

[0117] Hydrogen peroxide (manufactured by Wako Pure Chemical Industries, Ltd.), diethylenetriaminepenta(methylenephosphonic acid) 7 sodium salt (32 % aqueous solution) (manufactured by Italmatch Japan Co., Ltd.), potassium hydroxide (manufactured by Wako Pure Chemical Industries, Ltd.), and citric acid (manufactured by Komatsuya Co., Ltd.), were stirred appropriately to obtain the etchant of the present invention. The obtained etchant had a pH of 9.0. This etchant was referred to as etchant 1.

experiment example 1～3

[0125] Experimental example 1-3 Immersion test of etchant 1-3

[0126] Each etchant obtained in Example 1 and Comparative Examples 1-2 was filled in a polypropylene container, and a 1 cm x 2 cm titanium plate (manufactured by RAREMETALLIC) and a 2 cm x 2 cm titanium plate were placed in the etchant heated to 40° C. One copper plate (manufactured by Rare Metallic Co., Ltd.) of 2 cm was dipped simultaneously for 300 minutes. During etching, 100 μL for metal content analysis and 100 μL for hydrogen peroxide analysis were sampled at predetermined intervals (30, 60, 180, and 300 minutes).

[0127] Each etchant sampled for metal content analysis was diluted 100 times with 1% nitric acid aqueous solution, and metal titanium and metal copper were measured using a plasma emission spectrometer (device name: ICP-AESSPS-3100; manufactured by SII Corporation). content. The dissolved amounts of metal titanium and metal copper per unit area of ​​the titanium plate and the copper plate, and...

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Abstract

The objective of the present invention is to provide: an etching agent for a titanium-based metal on a semiconductor substrate, which is suppressed in decomposition of hydrogen peroxide, has a long service life, and has less need for control of the hydrogen peroxide concentration in the etching agent even in cases where the etching agent is used for a semiconductor substrate that has a titanium-based metal and copper metal or a copper alloy; an etching method; and an etching agent preparation liquid which is mixed with hydrogen peroxide for use. The present invention relates to: an etching agent for a titanium-based metal on a semiconductor substrate which has the titanium-based metal and copper metal or a copper alloy arranged on top of the titanium-based metal, said etching agent being an aqueous solution that contains at least (A) hydrogen peroxide, (B) a phosphonic acid-based chelating agent having a nitrogen atom in the structure, (C) an alkali metal hydroxide and (D) an organic acid having at least one hydroxyl group and at least three carboxyl groups; an etching method which is characterized by using this etching agent; and an etching agent preparation liquid which is mixed with hydrogen peroxide for use.

Description

technical field [0001] The present invention relates to the processing of titanium-based metals in semiconductor substrates having titanium (sometimes abbreviated as Ti)-based metals, and more specifically, to processing of titanium-based metals with, for example, metal titanium, titanium-tungsten (hereinafter sometimes abbreviated as TiW) alloys, etc. An etchant, an etching method, and the like for titanium-based metals and copper or copper alloy semiconductor substrates located on top of the titanium-based metals. Background technique [0002] In response to market demands such as high performance and miniaturization, semiconductor devices represented by silicon semiconductors are being miniaturized and highly integrated. With miniaturization and high integration, copper having a low wiring resistance is mainly used as a metal for forming a fine wiring pattern. As a barrier layer against such copper wiring, a metal layer (metal film) made of metal titanium, a metal layer ...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): H01L21/308C23F1/38H01L21/306
CPCC23F1/38H01L21/32134
Inventor 横沟贵宏鹤本浩之柿泽政彦
Owner FUJIFILM CORP
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