WO2020042223A1

WO2020042223A1 - Etching solution composition for copper/molybdenum film layer

Info

Publication number: WO2020042223A1
Application number: PCT/CN2018/105231
Authority: WO
Inventors: 赵芬利
Original assignee: 深圳市华星光电技术有限公司
Priority date: 2018-08-31
Filing date: 2018-09-12
Publication date: 2020-03-05
Also published as: CN109023372A

Abstract

An etching solution composition for a copper/molybdenum film layer, comprising a homogeneous mixture of an oxidizing agent, an organic acid, an etching regulator, an inorganic salt, a chelating agent, an etching inhibitor, and a solvent. Relative to the total mass of the composition, the oxidizing agent has a mass fraction of 5% to 15%, the organic acid has a mass fraction of 4% to 13%, the etching regulator has a mass fraction of 0.1% to 5%, the inorganic salt has a mass fraction of 0.1% to 5%, the chelating agent has a mass fraction of 0.5% to 9%, the etching inhibitor has a mass fraction of 0.001% to 1%, and the remaining is the solvent.

Description

Etchant composition for copper / molybdenum film layer

Technical field

The invention relates to the field of copper process etching, in particular to an etching solution composition for a copper / molybdenum film layer.

Background technique

In recent years, with the increase in the demand for displays, people have put forward higher requirements for product quality and screen accuracy, and the quality of the etching effect directly affects the quality of the circuit board manufacturing process, and then affects the display image. quality. As the size of the display increases, the length of metal wirings such as gate lines and data lines connected to the thin film transistors will increase, and the resistance of the metal wirings will increase, which will cause problems such as signal delay.

At present, the metal wiring of the display usually uses copper metal. Compared with aluminum metal, copper has a low resistance value and excellent processability. The width of the copper wire does not need to reach the width of the aluminum wire, which can improve the penetration of the display and The efficiency of the backlight source makes copper wires more suitable for the production of high-resolution panels.

The formation of the copper process pattern in the display panel is generally: firstly forming a copper / molybdenum film on the substrate, molybdenum can increase the adhesion of copper to the substrate, and at the same time can prevent the diffusion of copper on the substrate; then it can be formed on the copper / molybdenum film A photoresist in a predetermined pattern; thereafter, the copper / molybdenum film is etched with an etchant to form a metal circuit. However, the conventional fluorine-containing etching solution is corrosive, has low etching efficiency, poor stability, and is unfriendly to the environment.

technical problem

The invention provides an etching solution composition for a copper / molybdenum film layer to solve the existing etching solution, which contains fluoride, has a negative impact on the device and the environment, and has a low etching efficiency, thereby affecting the technical problems of display.

Technical solutions

To solve the above problems, the technical solution provided by the present invention is as follows:

The invention provides an etching solution composition for a copper / molybdenum film layer, comprising: a uniformly mixed oxidant, organic acid, etching regulator, inorganic salt, chelating agent, etching inhibitor, and deionized water; The mass of the composition, the mass fraction of the oxidant is 5% to 15%, the mass fraction of the organic acid is 4% to 13%, the mass fraction of the etching conditioner is 0.1% to 5%, and the inorganic The mass fraction of the salt is 0.1% to 5%, the mass fraction of the chelating agent is 0.5% to 9%, the mass fraction of the etching inhibitor is 0.001% to 1%, and the balance is the deionized water.

In at least one embodiment of the present invention, the oxidant is hydrogen peroxide.

In at least one embodiment of the present invention, the organic acid is selected from the group consisting of acetic acid, glycolic acid, 2-hydroxypropane-1,2,3-tricarboxylic acid, benzoic acid, oxalic acid, succinic acid, 2, At least one of 3-dihydroxysuccinic acid, 2-hydroxysuccinic acid, 2-hydroxypropionic acid, and phthalic acid.

In at least one embodiment of the present invention, the etching modifier is an amine compound.

In at least one embodiment of the present invention, the etching modifier is selected from at least one of diisopropanolamine, polyacrylamide, m-phenylenediamine, p-chloroaniline, and monoisopropanolamine.

In at least one embodiment of the present invention, the inorganic salt is selected from at least one of a sodium salt, a magnesium salt, and a potassium salt.

In at least one embodiment of the present invention, the inorganic salt is selected from the group consisting of sodium chloride, magnesium chloride, potassium chloride, sodium sulfate, magnesium sulfate, potassium sulfate, sodium nitrate, magnesium nitrate, potassium nitrate, sodium acetate, and magnesium acetate. At least one of potassium acetate.

In at least one embodiment of the present invention, the chelating agent is selected from at least one of sodium stannate, sodium pyrophosphate, 8-hydroxyquinoline, and chitosan.

In at least one embodiment of the present invention, the etching inhibitor is selected from the group consisting of 6-nitrobenzimidazole, 2-aminothiazole, 2-amino-5-nitrothiazole, 5-aminotetrazole, 3- At least one of amino-1,2,4-triazole, benzotriazole, benzotriazole, sodium azole triazole, and sulfobenzotriazole.

The invention also provides an etching solution composition for a copper / molybdenum film layer, including:

Mix uniformly oxidant, organic acid, etching regulator, inorganic salt, chelating agent, etching inhibitor, and solvent;

Wherein, relative to the mass of the overall composition, the mass fraction of the oxidant is 5% to 15%, the mass fraction of the organic acid is 4% to 13%, and the mass fraction of the etching conditioner is 0.1% to 5 %, The mass fraction of the inorganic salt is 0.1% to 5%, the mass fraction of the chelating agent is 0.5% to 9%, the mass fraction of the etching inhibitor is 0.001% to 1%, and the balance is the Solvent.

Beneficial effect

The beneficial effects of the present invention are: the etching solution composition for the copper / molybdenum film layer provided by the present invention reduces the influence of the chemical solution on the environment and the device, and improves the etching efficiency and etching stability.

BRIEF DESCRIPTION OF THE DRAWINGS

In order to more clearly explain the embodiments or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings in the following description are merely inventions. For some embodiments, for those skilled in the art, other drawings can be obtained based on these drawings without paying creative labor.

1 is a schematic cross-sectional view of a copper / molybdenum film layer when an etching solution composition of the present invention is etched;

2 is an electron micrograph of a copper / molybdenum film layer when the etchant composition of the first embodiment of the present invention is etched;

FIG. 3 is another electron microscope image of the copper / molybdenum film layer when the etchant composition of Embodiment 1 of the present invention is etched.

Embodiments of the invention

The following descriptions of the embodiments are made with reference to additional illustrations to illustrate specific embodiments in which the present invention can be implemented. The directional terms mentioned in the present invention, such as [up], [down], [front], [rear], [left], [right], [in], [out], [side], etc., are for reference only. The direction of the attached schema. Therefore, the directional terms used are for explaining and understanding the present invention, but not for limiting the present invention. In the figure, similarly structured units are denoted by the same reference numerals.

The present invention is directed to the existing etching solution, because it contains fluoride, which has a negative impact on the environment and devices, and has a low etching efficiency. This embodiment can solve this defect.

The invention provides an etching solution composition for a copper / molybdenum film layer, comprising: an oxidant, an organic acid, an etching regulator, an inorganic salt, a chelating agent, an etching inhibitor, and a solvent, which are uniformly mixed.

The etching temperature of the etching solution composition is 25 to 35 degrees Celsius, and at this temperature, the etching effect is better.

The oxidant is hydrogen peroxide, and the solvent is deionized water.

The organic acid is selected from the group consisting of acetic acid, glycolic acid, 2-hydroxypropane-1,2,3-tricarboxylic acid, benzoic acid, oxalic acid, succinic acid, 2,3-dihydroxysuccinic acid, and 2-hydroxyl. At least one of succinic acid, 2-hydroxypropionic acid, and phthalic acid.

The etching regulator is an amine compound. Specifically, the etching regulator may be one or more of diisopropanolamine, polyacrylamide, m-phenylenediamine, p-chloroaniline, and monoisopropanolamine. In a combination, when etching is performed, the etching rate of the copper / molybdenum film layer can be adjusted by adjusting the content of the etching inhibitor in the etching solution composition, so that the film layer has an etching profile with an appropriate taper angle.

The inorganic salt may be one or more combinations of inorganic sodium salt, inorganic magnesium salt, and inorganic potassium salt. Specifically, the inorganic salt may be sodium chloride, magnesium chloride, potassium chloride, sodium sulfate, magnesium sulfate, One or more combinations of potassium sulfate, sodium nitrate, magnesium nitrate, potassium nitrate, sodium acetate, magnesium acetate, potassium acetate.

The chelating agent is selected from one or more of sodium stannate, sodium pyrophosphate, 8-hydroxyquinoline, and chitosan.

The etching inhibitor is selected from 6-nitrobenzimidazole, 2-aminothiazole, 2-amino-5-nitrothiazole, 5-aminotetrazole, 3-amino-1,2,4-triazole, At least one of benzotriazole, benzotriazole, sodium azole triazole, and sulfobenzotriazole.

The following description is made with reference to specific embodiments.

The etching solution composition for the copper / molybdenum film layer provided in this embodiment includes: hydrogen peroxide, 2-hydroxypropane-1,2,3-tricarboxylic acid, diisopropanolamine, 8-hydroxyquinoline, and chlorination. Sodium, benzotriazole.

As shown in Table 1, Table 1 is a composition table of the etching solution composition. With respect to the mass of the entire etching solution composition, the mass fraction of each component is: hydrogen peroxide 10%, 2-hydroxypropane-1 8% of 2,3-tricarboxylic acid, 3% of diisopropanolamine, 2.5% of 8-hydroxyquinoline, 0.5% of sodium chloride, 0.02% of benzotriazole and 75.98% of deionized water.

Table 1

组分 Component	氧化物 Oxide	有机酸 Organic acid	蚀刻调节剂 Etching modifier	螯合剂 Chelating agent	无机盐 Inorganic salt	蚀刻抑制剂 Etching inhibitor	溶剂 Solvent
物质 Matter	过氧化氢 hydrogen peroxide	2-羟基丙烷-1,2,3-三羧酸 2-hydroxypropane-1,2,3-tricarboxylic acid	二异丙醇胺 Diisopropanolamine	8-羟基喹啉 8-hydroxyquinoline	氯化钠 Sodium chloride	苯骈三氮唑 Benzotriazole	去离子水 Deionized water
质量分数 Quality score	10% 10%	8% 8%	3% 3%	2.50% 2.50%	0.50% 0.50%	0.02% 0.02%	75.98% 75.98%

As shown in FIG. 1, when a copper / molybdenum film layer is generally etched, a device having a copper / molybdenum film layer is contacted with an etching solution. The device includes a substrate 11, a copper / molybdenum film layer 12, and a photoresist. 13.

The etching solution with good performance can suppress the side etching amount of the film layer, so that the cross-sectional shape of the film layer after the etching is within a predetermined range. Generally speaking, the taper angle α formed by the side etched surface of the end of the etched copper / molybdenum film layer 12 and the plane on which the substrate 11 is located is preferably 30-60 degrees, and the photoresist 13 on the same side The vertical distance m (CD Loss) from the endpoint of the lower surface to the endpoint of the lower surface of the copper-molybdenum film layer 12 is preferably less than 1 micron.

As shown in Figure 2, under the condition of an etching temperature of 35, the etched film was observed using a scanning electron microscope (SEM). The data showed that the cone angle α was 46.2 degrees and the CD Loss was 0.78 microns, as shown in Figure 3. It is shown that there is no molybdenum remaining on the film layer after being etched by using the etchant composition of this embodiment. It can be seen that the etching effect of the etching solution composition provided by the present invention is good.

Beneficial effect: The etching solution composition for the copper / molybdenum film layer provided by the present invention reduces the influence of the chemical solution on the environment and devices, and improves the etching efficiency and etching stability.

In summary, although the present invention has been disclosed as above with preferred embodiments, the above preferred embodiments are not intended to limit the present invention. Those skilled in the art can make various modifications without departing from the spirit and scope of the present invention. This kind of modification and retouching, therefore, the protection scope of the present invention is subject to the scope defined by the claims.

Claims

An etching solution composition for a copper / molybdenum film layer, comprising:

Mix uniformly oxidant, organic acid, etching regulator, inorganic salt, chelating agent, etching inhibitor, and deionized water;

Wherein, relative to the mass of the overall composition, the mass fraction of the oxidant is 5% to 15%, the mass fraction of the organic acid is 4% to 13%, and the mass fraction of the etching conditioner is 0.1% to 5 %, The mass fraction of the inorganic salt is 0.1% to 5%, the mass fraction of the chelating agent is 0.5% to 9%, the mass fraction of the etching inhibitor is 0.001% to 1%, and the balance is the Deionized water.
The etching solution composition according to claim 1, wherein the oxidant is hydrogen peroxide.
The etching solution composition according to claim 1, wherein the organic acid is selected from the group consisting of acetic acid, glycolic acid, 2-hydroxypropane-1,2,3-tricarboxylic acid, benzoic acid, oxalic acid, and succinic acid. At least one of 2,3-dihydroxysuccinic acid, 2-hydroxysuccinic acid, 2-hydroxypropionic acid, and phthalic acid.
The etching solution composition according to claim 1, wherein the etching conditioner is an amine compound.
The etching solution composition according to claim 4, wherein the etching modifier is selected from at least one of diisopropanolamine, polyacrylamide, m-phenylenediamine, p-chloroaniline, and monoisopropanolamine. .
The etching solution composition according to claim 1, wherein the inorganic salt is at least one selected from a sodium salt, a magnesium salt, and a potassium salt.
The etching solution composition according to claim 6, wherein the inorganic salt is selected from the group consisting of sodium chloride, magnesium chloride, potassium chloride, sodium sulfate, magnesium sulfate, potassium sulfate, sodium nitrate, magnesium nitrate, potassium nitrate, and sodium acetate. , Magnesium acetate, potassium acetate.
The etching solution composition according to claim 1, wherein the chelating agent is at least one selected from the group consisting of sodium stannate, sodium pyrophosphate, 8-hydroxyquinoline, and chitosan.
The etching solution composition according to claim 1, wherein the etching inhibitor is selected from the group consisting of 6-nitrobenzimidazole, 2-aminothiazole, 2-amino-5-nitrothiazole, and 5-aminotetrazole. , At least one of 3-amino-1,2,4-triazole, benzotriazole, benzotriazole, sodium oxazolium, and sulfobenzotriazole.
An etching solution composition for a copper / molybdenum film layer, comprising:

Mix uniformly oxidant, organic acid, etching regulator, inorganic salt, chelating agent, etching inhibitor, and solvent;

Wherein, relative to the mass of the overall composition, the mass fraction of the oxidant is 5% to 15%, the mass fraction of the organic acid is 4% to 13%, and the mass fraction of the etching conditioner is 0.1% to 5 %, The mass fraction of the inorganic salt is 0.1% to 5%, the mass fraction of the chelating agent is 0.5% to 9%, the mass fraction of the etching inhibitor is 0.001% to 1%, and the balance is the Solvent.
The etching solution composition according to claim 10, wherein the oxidant is hydrogen peroxide.
The etching solution composition according to claim 10, wherein the organic acid is selected from the group consisting of acetic acid, glycolic acid, 2-hydroxypropane-1,2,3-tricarboxylic acid, benzoic acid, oxalic acid, and succinic acid. At least one of 2,3-dihydroxysuccinic acid, 2-hydroxysuccinic acid, 2-hydroxypropionic acid, and phthalic acid.
The etching solution composition according to claim 10, wherein the etching modifier is an amine compound.
The etching solution composition according to claim 13, wherein the etching modifier is selected from at least one of diisopropanolamine, polyacrylamide, m-phenylenediamine, p-chloroaniline, and monoisopropanolamine. .
The etching solution composition according to claim 10, wherein the inorganic salt is at least one selected from a sodium salt, a magnesium salt, and a potassium salt.
The etching solution composition according to claim 15, wherein the inorganic salt is selected from the group consisting of sodium chloride, magnesium chloride, potassium chloride, sodium sulfate, magnesium sulfate, potassium sulfate, sodium nitrate, magnesium nitrate, potassium nitrate, and sodium acetate. , Magnesium acetate, potassium acetate.
The etching solution composition according to claim 10, wherein the chelating agent is at least one selected from the group consisting of sodium stannate, sodium pyrophosphate, 8-hydroxyquinoline, and chitosan.
The etching solution composition according to claim 10, wherein the etching inhibitor is selected from the group consisting of 6-nitrobenzimidazole, 2-aminothiazole, 2-amino-5-nitrothiazole, and 5-aminotetrazole. , At least one of 3-amino-1,2,4-triazole, benzotriazole, benzotriazole, sodium oxazolium, and sulfobenzotriazole.