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CN-122013188-A - One-step etching solution for Cu alloy oxide and preparation method thereof

CN122013188ACN 122013188 ACN122013188 ACN 122013188ACN-122013188-A

Abstract

The invention relates to the technical field of etching solutions, in particular to a one-step etching solution for Cu alloy oxide and a preparation method thereof, wherein the one-step etching solution comprises a main agent and an auxiliary agent, the main agent at least comprises, by mass, 4.00-8.00% of hydrogen peroxide, 0.50-14.00% of organic acid, 0-2.2% of pH regulator, 0.03-0.4% of fluorine-containing compound, 0.50-1.00% of stabilizer, 0.50-2.00% of organic base, 0.20-0.50% of inhibitor, 0-1% of purine-containing compound and the balance of deionized water, and the auxiliary agent at least comprises auxiliary organic acid, auxiliary pH regulator, auxiliary fluorine-containing compound, auxiliary organic base, auxiliary inhibitor, auxiliary stabilizer and deionized water. Through system optimization, copper alloy and oxide are etched in one step under the condition of low hydrogen peroxide, and the problems of alloy layer chamfering, IGZO without vertical side wall/sharp Tip and the like are solved.

Inventors

  • WU SICHENG
  • LIU MINGMING
  • LI CHUANG
  • ZHANG HONGWEI
  • HUANG HAIDONG
  • HU TIANQI

Assignees

  • 南京和显达微电子科技有限公司

Dates

Publication Date
20260512
Application Date
20260206

Claims (10)

  1. 1. A one-step etching solution for Cu alloy oxide is characterized by comprising a main agent and an auxiliary agent, wherein the main agent at least comprises, by mass, 4.00-8.00% of hydrogen peroxide, 0.50-14.00% of organic acid, 0-2.2% of pH regulator, 0.03-0.4% of fluorine-containing compound, 0.50-1.00% of stabilizer, 0.50-2.00% of organic base, 0.20-0.50% of inhibitor, 0-1% of purine group-containing compound and the balance of deionized water, and the auxiliary agent at least comprises auxiliary organic acid, auxiliary pH regulator, auxiliary fluorine-containing compound, auxiliary organic base, auxiliary inhibitor, auxiliary stabilizer and deionized water.
  2. 2. The Cu-alloy oxide one-step etching etchant of claim 1, wherein the auxiliary agent comprises, by mass, at least 16.00-30.00% of an auxiliary organic acid, 7.00-20.00% of an auxiliary pH adjuster, 0-5.00% of an auxiliary fluorine-containing compound, 0-10.00% of an auxiliary organic base, 1.50-2.00% of an auxiliary inhibitor, 0-1.00% of an auxiliary stabilizer, and deionized water, the balance being the etchant.
  3. 3. The Cu-alloy oxide one-step etching etchant of claim 1, wherein the organic acid and the co-organic acid are each at least one selected from malonic acid, iminodiacetic acid, citric acid, glutamic acid, glycine, or lactic acid.
  4. 4. The Cu alloy oxide one-step etching etchant of claim 1, wherein the organic base and the auxiliary organic base are each selected from at least one of isopropanolamine, dimethylethanolamine, triethanolamine, diethylaminopropylamine, or tetramethylammonium hydroxide.
  5. 5. The Cu alloy oxide one-step etching etchant of claim 1, wherein the pH adjustor and the auxiliary pH adjustor are each selected from at least one of ammonium bisulfate, nitric acid, or phenolsulfonic acid.
  6. 6. The Cu alloy oxide one-step etching etchant of claim 1, wherein the fluorine-containing compound or the auxiliary fluorine-containing compound is selected from ammonium bifluoride and hydrofluoric acid.
  7. 7. The Cu alloy oxide one-step etching etchant of claim 1, wherein the stabilizer and the auxiliary stabilizer are each selected from at least one of polyethylene glycol, 1, 3-propanediol, or ethylene glycol butyl ether.
  8. 8. The Cu-alloy oxide one-step etching etchant of claim 1, wherein the inhibitor and the co-inhibitor are each at least one selected from the group consisting of 5-methyltetrazole, 5-aminotetrazole, 3-amino-1, 2, 4-triazole, vitamin B4, and tetramethylurea.
  9. 9. The Cu alloy oxide one-step etching etchant of claim 1, wherein the purine group-containing compound is selected from at least one of 7H-purine or 3-methylxanthine.
  10. 10. A method for preparing a Cu alloy oxide one-step etching solution according to any one of claims 1 to 9, comprising at least the steps of mixing the raw materials of the main agent to prepare the main agent, and mixing the preparation raw materials of the auxiliary agent to prepare the auxiliary agent.

Description

One-step etching solution for Cu alloy oxide and preparation method thereof Technical Field The invention relates to the technical field of etching solutions, in particular to a Cu alloy oxide one-step etching solution and a preparation method thereof. Background At present, hydrogen peroxide (H 2O2) is a key oxidant in the etching liquid on the market and is used for oxidizing metal and adjusting etching rate, but the chemical property of the etching liquid is unstable, gas production and heat release are easy to decompose, explosion risks exist, and concentration fluctuation can influence process stability. In addition, when used for etching multilayer films, the density, chemical bonding and etching mechanism of different film layers are different, so that the etching rates of the film layers in the conventional etching solution are significantly different. When the etch rates are not matched, the faster film forms "undercuts" (Undercut), while the slower film forms "vertical" sidewalls or sharp "tips" that are prone to metal under fill or Tip discharge in subsequent processes. Taiwan patent application publication No. TW201311934a discloses a method for manufacturing a display device and an etchant composition for a metal layer containing copper/metal oxide layer, which provide an etchant composition for simultaneously etching copper metal and metal oxide layers by using persulfate, fluorine compound, inorganic acid, cyclic amine compound, chlorine compound and organic acid, preventing excessive cutting and improving process reliability. But cannot have high safety and environmental friendliness on the premise of ensuring excellent etching morphology (no vertical side wall/sharp Tip) and wide process window. Disclosure of Invention In order to solve the problems, the invention provides a one-step etching solution for Cu alloy oxide, which realizes one-step etching of the Cu alloy and the oxide under the condition of low hydrogen peroxide through system optimization, and solves the problems of chamfering of an alloy layer, no vertical side wall/sharp Tip of IGZO (indium gallium zinc oxide) and the like. The invention provides a Cu alloy oxide one-step etching solution which comprises a main agent and an auxiliary agent, wherein the main agent at least comprises, by mass, 4.00-8.00% of hydrogen peroxide, 0.50-14.00% of organic acid, 0-2.2% of pH regulator, 0.03-0.4% of fluorine-containing compound, 0.50-1.00% of stabilizer, 0.50-2.00% of organic base, 0.20-0.50% of inhibitor, 0-1% of purine group-containing compound and the balance of deionized water, and the auxiliary agent at least comprises auxiliary organic acid, auxiliary pH regulator, auxiliary fluorine-containing compound, auxiliary organic base, auxiliary inhibitor, auxiliary stabilizer and deionized water. In one embodiment, the auxiliary agent at least comprises 16.00-30.00% of auxiliary organic acid, 7.00-20.00% of auxiliary pH regulator, 0-5.00% of auxiliary fluorine-containing compound, 0-10.00% of auxiliary organic alkali, 1.50-2.00% of auxiliary inhibitor, 0-1.00% of auxiliary stabilizer and the balance of deionized water according to mass percentage. In one embodiment, the organic acid and the auxiliary organic acid are each selected from at least one of malonic acid, iminodiacetic acid, citric acid, glutamic acid, glycine, or lactic acid. In one embodiment, the organic base and the auxiliary organic base are each selected from at least one of isopropanolamine, dimethylethanolamine, triethanolamine, diethylaminopropylamine, or tetramethylammonium hydroxide. In one embodiment, the pH adjustor and the auxiliary pH adjustor are each selected from at least one of ammonium bisulfate, nitric acid, or phenolsulfonic acid. In one embodiment, the fluorine-containing compound or the auxiliary fluorine-containing compound is selected from ammonium bifluoride or hydrofluoric acid. In one embodiment, the stabilizer and the auxiliary stabilizer are each selected from at least one of polyethylene glycol, 1, 3-propanediol, or ethylene glycol butyl ether. In one embodiment, the inhibitor and the co-inhibitor are each selected from at least one of 5-methyltetrazole, 5-aminotetrazole, 3-amino-1, 2, 4-triazole, vitamin B4, or tetramethylurea. In one embodiment, the purine-containing compound is selected from at least one of 7H-purine or 3-methylxanthine. In one embodiment, the purine group containing compound is added in an amount of 0 to 0.5%. In one embodiment, the purine group containing compound is added in an amount of 0 to 0.1%. According to the invention, the addition amount of hydrogen peroxide in the system is optimized to be 4.00-8.00%, and the fluorine-containing compound and other reagents are matched, so that the oxidation side reaction is reduced, the safety is improved, the Cu oxidation rate and the IGZO etching rate are synchronous, and the etching effect is ensured. Furthermore, the invention adopts the optimized organic acid system to be mat