CN113430065B

CN113430065B - Composition for removing residues after cleaning and etching of anti-reflection coating, preparation method and application

Info

Publication number: CN113430065B
Application number: CN202010210656.1A
Authority: CN
Inventors: 王溯; 蒋闯; 李国山
Original assignee: Shanghai Xinyang Semiconductor Material Co Ltd
Current assignee: Shanghai Xinyang Semiconductor Material Co Ltd
Priority date: 2020-03-23
Filing date: 2020-03-23
Publication date: 2024-06-07
Anticipated expiration: 2040-03-23
Also published as: CN113430065A

Abstract

The invention discloses an anti-reflection coating cleaning and etching residue removing composition, a preparation method and application thereof. The composition is prepared from the following raw materials in parts by mass: 0.1% -4% of fluoride, 0.5% -6% of quaternary ammonium base, 0.005% -3% of chelating agent, 0.005% -3% of corrosion inhibitor, 10% -30% of organic amine, 0.005% -3% of surfactant, 0.005% -2% of passivating agent, 5% -50% of organic solvent and the balance of water; wherein the surfactant is EO-PO polymer L31, and the passivating agent is 1- (benzotriazole-1-methyl) -1- (2-methylbenzimidazole). The composition has strong corrosion inhibition on various metal materials, dielectric materials and SARC materials and good cleaning effect.

Description

Composition for removing residues after cleaning and etching of anti-reflection coating, preparation method and application

Technical Field

The invention relates to an anti-reflection coating cleaning and etching residue removing composition, a preparation method and application thereof.

Background

DUV lithography is a relatively advanced lithography technique in the chip manufacturing process, and the high reflectivity of DUV wavelengths results in the reflection of DUV radiation back into the photoresist, thereby creating standing waves in the photoresist layer. The standing wave further triggers photochemical reactions in the photoresist, causing uneven photoresist exposure, including portions of the mask that are not intended to be exposed to radiation, which results in variations in line widths, spacing, and other critical dimensions. Dual and tri-layer photoresists, bottom antireflective coatings (BARCs) and sacrificial antireflective coatings (SARCs) have been developed to address the transmittance and reflectance issues and are applied to substrates prior to photoresist application. All of these antireflective coatings have a planarizing effect on the topological wafer surface encountered in typical dual damascene integration, and all incorporate UV chromophores into spin-on polymer matrices that will absorb incident UV radiation.

In the chip manufacturing technology, the residual cleaning liquid after the plasma etching of the copper interconnection is mainly fluorine-containing cleaning liquid. With the continuous advancement of technology nodes, more and more materials are introduced, such as titanium, tungsten, titanium nitride and other metal materials, low-k dielectric materials and the like, so that the compatibility of the traditional fluorine-containing cleaning solution with various materials is challenging. The fluorine-containing cleaning solution should be compatible with etching of metal materials (e.g., co, cu, W) and dielectric materials (e.g., TEOS, siN, high-k, low-k) without loss of these materials while providing ARC removal.

Disclosure of Invention

The invention aims to overcome the defects of poor compatibility and corrosion inhibition performance, poor cleaning effect and the like of the existing microelectronic device cleaning liquid with an anti-reflection material and/or residues after etching on the metal material and the dielectric material, and provides an anti-reflection coating cleaning and post-etching residue removal composition, a preparation method and application. The composition has strong corrosion inhibition on various metal materials, dielectric materials and SARC materials and good cleaning effect.

The invention solves the technical problems through the following technical proposal.

The invention provides a composition which is prepared from the following raw materials in parts by mass: 0.1% -4% of fluoride, 0.5% -6% of quaternary ammonium base, 0.005% -3% of chelating agent, 0.005% -3% of corrosion inhibitor, 10% -30% of organic amine, 0.005% -3% of surfactant, 0.005% -2% of passivating agent, 5% -50% of organic solvent and the balance of water, wherein the mass fraction of each component accounts for the total mass of the raw materials;

wherein the surfactant is EO-PO polymer L31, and the passivating agent is 1- (benzotriazole-1-methyl) -1- (2-methylbenzimidazole).

In the composition, the fluoride may be fluoride conventionally used in the art, preferably one or more of hydrofluoric acid, ammonium fluoride, tetramethyl ammonium fluoride, hydrogen ammonium fluoride, fluorosilicic acid and sodium fluoride, more preferably ammonium fluoride and/or hydrogen ammonium fluoride.

The mass fraction of fluoride in the composition may be from 0.1% to 3%, preferably from 0.5% to 3% (e.g. 0.5%, 1% or 3%).

In the composition, the quaternary ammonium base may be one or more of quaternary ammonium bases conventionally used in the art, preferably tetramethyl ammonium hydroxide, tetrapropyl ammonium hydroxide, tetrabutyl ammonium hydroxide, tetraethyl ammonium hydroxide (TEAH), benzyl Trimethyl Ammonium Hydroxide (BTAH), choline, (2-hydroxyethyl) trimethyl ammonium hydroxide, tris (2-hydroxyethyl) methyl ammonium hydroxide, monoethanolamine (MEA), diglycolamine (DGA), triethanolamine (TEA), isobutolamine, isopropanolamine, tetrabutyl phosphonium hydroxide (TBPH) phosphorus, and tetramethyl guanidine, more preferably tetramethyl ammonium hydroxide and/or choline.

The mass fraction of the quaternary ammonium base in the composition may be 0.5% to 5%, preferably 1% to 5% (e.g. 1%, 2.5% or 5%).

The chelating agent in the composition may be a chelating agent conventionally used in the art, preferably 1, 2-cyclohexanediamine-N, N, N ', N' -tetraacetic acid (CDTA), ethylenediamine tetraacetic acid, nitrilotriacetic acid, diethylenetriamine pentaacetic acid, 1,4,7, 10-tetraazacyclododecane-1, 4,7, 10-tetraacetic acid, ethylene Glycol Tetraacetic Acid (EGTA), 1, 2-bis (o-aminophenoxy) ethane-N, N, N ', one or more of N' -tetraacetic acid, N- {2- [ bis (carboxymethyl) amino ] ethyl } -N- (2-hydroxyethyl) glycine (HEDTA), ethylenediamine-N, N '-bis (2-hydroxyphenylacetic acid) (EDDHA), dioxaoctamethylenediaza tetraacetic acid (DOCTA) and triethylenetetramine hexaacetic acid (TTHA), more preferably ethylenediamine tetraacetic acid and/or 1, 2-cyclohexanediamine-N, N' -tetraacetic acid (CDTA).

The chelating agent may be present in the composition in a mass fraction of 0.005% to 2%, preferably 0.01% to 2% (e.g. 0.01%, 0.5%, 1% or 2%).

In the composition, the corrosion inhibitor can be a corrosion inhibitor conventionally used in the art, preferably Benzotriazole (BTA), tolyltriazole, 5-phenyl-benzotriazole, 5-nitro-benzotriazole, 3-amino-5-mercapto-1, 2, 4-triazole, 1-amino-1, 2, 4-benzotriazole, hydroxybenzotriazole, 2- (5-amino-pentyl) -benzotriazole, 1-amino-1, 2, 3-triazole, 1-amino-5-methyl-1, 2, 3-triazole, 3-amino-1, 2, 4-triazole, 3-mercapto-1, 2, 4-triazole, 3-isopropyl-1, 2, 4-triazole, 5-thiophen-benzotriazole, halo-benzotriazole (halogen=F, cl, br or I), naphthotriazole 2-Mercaptobenzimidazole (MBI), 2-mercaptobenzothiazole, 4-methyl-2-phenylimidazole, 2-mercaptothiazoline, 5-aminotetrazole monohydrate, 5-amino-1, 3, 4-thiadiazole-2-thiol, 2, 4-diamino-6-methyl-1, 3, 5-triazine, thiazole, triazine, methyltetrazole, 1, 3-dimethyl-2-imidazolidinone, 1, 5-pentamethylene tetrazole, 1-phenyl-5-mercaptotetrazole, diaminomethyltriazine, imidazolinethione, mercaptobenzimidazole, 4-methyl-4H-1, 2, 4-triazole-3-thiol, one or more of 5-amino-1, 3, 4-thiadiazole-2-thiol and benzothiazole, more preferably Benzotriazole (BTA) and/or tolyltriazole.

The mass fraction of the corrosion inhibitor in the composition may be 0.005% to 2%, preferably 0.01% to 2% (e.g. 0.01%, 0.5%, 1% or 2%).

In the composition, the organic amine may be an organic amine conventionally used in the art, preferably one or more of monoethanolamine, diethanolamine, triethanolamine, diethanol monoisopropanolamine, N-methylethanolamine, isopropanolamine, ethyldiethanolamine, N-diethylethanolamine, N- (2-aminoethyl) ethanolamine and diglycolamine, more preferably monoethanolamine and/or isopropanolamine.

In the composition, the organic solvent may be an organic solvent conventionally used in the art, preferably tetramethylene sulfone, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, t-butanol, 1-pentanol, hexanol, cyclohexanol, 2-ethyl-1-hexanol, benzyl alcohol, furanmethanol, ethylene glycol, diethylene glycol, propylene glycol (1, 2-propanediol), tetramethylene glycol (1, 4-butanediol), 2, 3-butanediol, 1, 3-butanediol, neopentyl glycol, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, diethylene glycol monoethyl ether, triethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, propylene glycol methyl ether, dipropylene glycol methyl ether, tripropylene glycol methyl ether, propylene glycol n-propyl ether, dipropylene glycol n-propyl ether, tripropylene glycol n-butyl ether, dipropylene glycol n-butyl ether and tripropylene glycol n-butyl ether, dimethylacetamide, formamide, dimethylformamide, 1-methylpyrrolidone, dimethylsulfoxide, and one or more of methyl sulfones, preferably one or more of methyl sulfones.

The mass fraction of the organic solvent in the composition may be 10% -50% (e.g., 10%, 30% or 50%).

The mass fraction of the surfactant in the composition may be 0.005% to 2%, preferably 0.01% to 2% (e.g. 0.01%, 0.05%, 0.7% or 2%).

The mass fraction of the passivating agent in the composition may be 0.005% -1%, preferably 0.01% -1% (e.g. 0.01%, 0.05%, 0.7% or 2%).

In certain preferred embodiments of the present invention, the present invention provides a composition prepared from the following raw materials, the raw materials comprising the following components in parts by mass: 0.1% -3% of fluoride, 0.5% -5% of quaternary ammonium base, 0.005% -2% of chelating agent, 0.005% -2% of corrosion inhibitor, 10% -30% of organic amine, 0.005% -2% of surfactant, 0.005% -1% of passivating agent, 5% -50% of organic solvent and the balance of water, wherein the mass fraction of each component accounts for the total mass of the raw materials.

In certain preferred embodiments of the present invention, the present invention provides a composition prepared from the following raw materials, the raw materials comprising the following components in parts by mass: 0.5% -3% of fluoride, 1% -5% of quaternary ammonium base, 0.01% -2% of chelating agent, 0.01% -2% of corrosion inhibitor, 10% -30% of organic amine, 0.01% -2% of surfactant, 0.01% -1% of passivating agent, 10% -50% of organic solvent and the balance of water, wherein the mass percentages of the components are the total mass of the raw materials.

In certain preferred embodiments of the present invention, the present invention provides a composition made from the following raw materials, which are composed of the following components in mass fraction: the fluoride as described above, the quaternary ammonium base as described above, the chelating agent as described above, the corrosion inhibitor as described above, the organic amine as described above, the surfactant as described above, the passivating agent as described above, the organic solvent as described above and the balance of water, wherein the mass fraction is the mass percentage of each component to the total mass of the raw materials.

The invention also provides a preparation method of the composition, which comprises the following steps: mixing the raw materials to obtain a composition;

wherein, the mixing is preferably to add the solid component in the raw material components into the liquid component and stir the mixture uniformly.

In the preparation method, the temperature of the mixing may be room temperature.

The invention also provides the application of the composition in cleaning microelectronic devices with anti-reflection materials and/or residues after etching;

Wherein the microelectronic device having the anti-reflective material and/or post-etch residue thereon is preferably a patterned wafer having a patterned SARC structure;

Wherein the temperature of the washing is preferably 40 ℃ -60 ℃ (e.g. 50 ℃); the washing time may be 5min-30min (e.g., 20 min).

In the present invention, unless otherwise specified, "room temperature" means 10 to 40 ℃.

On the basis of conforming to the common knowledge in the field, the above preferred conditions can be arbitrarily combined to obtain the preferred examples of the invention.

The reagents and materials used in the present invention are commercially available.

The invention has the positive progress effects that: the compositions of the present invention are useful for cleaning microelectronic devices having antireflective materials thereon and/or post-etch residue containing, particularly for cleaning patterned wafers having patterned SARC structures, which are compatible with underlying dielectric materials, interconnect metals (e.g., aluminum, copper and cobalt alloys), and nitride-containing layers. In addition, the cleaning solution has strong corrosion inhibition on various metals (such as Co, W, cu and the like), dielectric materials (such as PECVD TEOS, CORAL ^TM, siN, tiON and the like) and SARC materials (such as DUO 248 ^TM or DUO 193 ^TM), and has no residue after cleaning a sample, good compatibility on various metals, dielectric materials and SARC materials and no undercut.

Detailed Description

The invention is further illustrated by means of the following examples, which are not intended to limit the scope of the invention. The experimental methods, in which specific conditions are not noted in the following examples, were selected according to conventional methods and conditions, or according to the commercial specifications.

1. Preparation examples of the compositions

The raw material components of table 1 were uniformly mixed according to the mass fraction of table 2 below. Wherein, the mixing is preferably to add the solid component in the raw material components into the liquid component and stir the mixture uniformly.

Table 1 kinds of components in examples

Wherein, the EO-PO materials are all purchased from Nantong Jinlai chemical industry Co.

TABLE 2 mass fractions of the components in the examples

2. Etching experiment

(1) Etching experiment operation:

The sample to be detected is statically immersed in the cleaning liquid for 20 minutes at 50 ℃, and then is cleaned by deionized water and then dried by nitrogen.

(2) Measuring etch rateThe method of (1):

the thickness of the sample before and after etching was measured separately, wherein the metal sample was measured for thickness using a four-point probe apparatus (CRESTEST-e of Japanese Napson), and the nonmetal sample was measured for thickness using an optical film thickness measuring apparatus (U.S. FILMETRICS F).

(3) Sample to be measured: a dummy wafer of a single material, such as copper, cobalt, dielectric material (low-k or high-k), SARC material, etc., is deposited on the silicon wafer. Among these are DUO 248 ^TM and DUO 193 ^TM, spin-on SARC materials (having a siloxane backbone containing organic light absorbing chromophores), commercially available from Honeywell ElectronicMaterials, commercially available for 248nm and 193nm photolithography, respectively. CORAL ^TM dielectric, OSG low-k dielectric material commercially available from Novellus Systems. PECVD TEOS, a silicon dioxide coating deposited by plasma enhanced chemical vapor deposition using tetraethyl orthosilicate.

Corrosion speed in the cleaning solutions of examples 1-12 and comparative examples 1-10As shown in table 3 below:

TABLE 3 Corrosion speed of sample dummy to be tested

3. Effect examples

Cleaning effect sample to be detected: a patterned wafer having a patterned SARC structure.

The cleaning effect experimental method comprises the following steps: the sample was statically immersed in a cleaning solution at 50 ℃ for 20 minutes, then deionized water was used for cleaning, and then nitrogen gas was used for drying. The cleaning and corrosion effects were observed with an electron microscope SEM.

TABLE 4 Effect example

Wherein, the cleaning effect is classified into four grades: a-no residue was observed; b-very little residue was observed; c-small residues were observed; d-significantly more residue was observed.

The corrosion effects are rated in four classes: a-compatibility is good, and undercut is avoided; b-very slight undercut; c-having a small undercut; d-undercut is more pronounced and severe.

In summary, in the above examples (1 to 12), no residue was observed after the sample to be tested was washed during the observation by an electron microscope, and the sample to be tested was excellent in compatibility with the composition of examples (1 to 12) and free from undercut. In the above comparative examples (1 to 10), residues were observed after washing the sample to be tested when observed by an electron microscope, and the sample to be tested was poor in compatibility in the compositions of comparative examples (1 to 10) and had an undercut phenomenon.

Claims

1. The composition is characterized by being prepared from the following raw materials in parts by mass: 0.5% -3% of fluoride, 1% -5% of quaternary ammonium base, 0.01% -2% of chelating agent, 0.01% -2% of corrosion inhibitor, 10% -30% of organic amine, 0.01% -2% of surfactant, 0.01% -1% of passivating agent, 10% -50% of organic solvent and the balance of water, wherein the mass percentages of the components are the total mass of the raw materials;

Wherein the surfactant is EO-PO polymer L31, and the passivating agent is 1- (benzotriazole-1-methyl) -1- (2-methylbenzimidazole);

the fluoride is ammonium fluoride and/or ammonium bifluoride;

the quaternary ammonium base is tetramethyl ammonium hydroxide and/or choline;

the chelating agent is ethylenediamine tetraacetic acid and/or 1, 2-cyclohexanediamine-N, N, N ', N' -tetraacetic acid;

The corrosion inhibitor is benzotriazole and/or tolyltriazole;

The organic amine is monoethanolamine and/or isopropanolamine;

the organic solvent is one or more of ethylene glycol monobutyl ether, tetramethylene sulfone and dimethylformamide.

2. The composition of claim 1 wherein the mass fraction of fluoride is 0.5%, 1% or 3%;

And/or the mass fraction of the quaternary ammonium base is 1%, 2.5% or 5%;

and/or the mass fraction of the chelating agent is 0.01%, 0.5%, 1% or 2%;

and/or, the mass fraction of the corrosion inhibitor is 0.01%, 0.5%, 1% or 2%;

And/or the mass fraction of the surfactant is 0.01%, 0.05%, 0.7% or 2%;

and/or the mass fraction of the passivating agent is 0.01%, 0.05%, 0.7% or 2%.

3. A process for the preparation of a composition as claimed in claim 1 or 2, comprising the steps of: mixing the above materials to obtain the final product.

4. The method for preparing the composition according to claim 3, wherein the mixing is carried out by adding the solid component of the raw material components into the liquid component and stirring uniformly;

and/or, the temperature of the mixing is room temperature.

5. Use of a composition according to claim 1 or 2 for cleaning microelectronic devices having antireflective material thereon and/or containing residues after etching.

6. The method of claim 5, wherein the microelectronic device having anti-reflective material and/or post-etch residue thereon is a patterned wafer having a patterned SARC structure.

7. Use of the composition according to claim 5 for cleaning microelectronic devices having antireflective material thereon and/or containing residues after etching, wherein the cleaning is at a temperature of 40 ℃ to 60 ℃;

and/or, the cleaning time is 5 min-30 min.

8. Use of the composition according to claim 6 for cleaning microelectronic devices having antireflective material thereon and/or containing residues after etching, wherein the cleaning is at a temperature of 50 ℃;

and/or, the cleaning time is 20 min.