KR20230165670A - Cleaning composition for removing residues on surfaces, metal-containing layer cleaning method using the same and semiconductor manufacturing method using the same - Google Patents

Abstract

A cleaning composition for removing surface residues, a method of cleaning a metal-containing film using the same, and a method of manufacturing a semiconductor device using the same are provided.

Description

Cleaning composition for removing residues on surfaces, metal-containing layer cleaning method using the same and semiconductor manufacturing method using the same}

It relates to a cleaning composition for removing surface residues, a method of cleaning a metal-containing film using the same, and a method of manufacturing a semiconductor device using the same.

In order to meet the excellent performance and low prices demanded by consumers, there is a need for increased integration and improved reliability of semiconductor devices. As the degree of integration of a semiconductor device increases, damage to the components of the semiconductor device during the manufacturing process has a greater impact on the reliability and electrical characteristics of the semiconductor memory device. In particular, during the manufacturing process of semiconductor devices, surface residues generated as a result of surface treatment (e.g., dry etching, etc.) on a certain film (e.g., metal-containing film) are used to form an additional layered film. It may cause peeling or cracks. Additionally, various chemical substances may be absorbed into the surface residue, which may cause the film existing around the surface residue to be further etched. Accordingly, the need for an effective cleaning process that removes substantially all of the surface residues and at the same time does not damage the surface of the film to be cleaned and does not cause defects in products containing metal-containing films is continuously increasing.

To provide a cleaning composition that can provide excellent cleaning power and at the same time does not damage the film to be cleaned, a method of cleaning a metal-containing film using the same, and a method of manufacturing a semiconductor device using the same.

According to one aspect,

Contains a solvent and a cleaning accelerator,

Contains no oxidizing agent,

The cleaning accelerator includes a salt represented by Formula 1A below, a salt represented by Formula 1B below, or a combination thereof, and a cleaning composition for removing residues on surfaces is provided:

<Formula 1A> <Formula 1B>

In formulas 1A and 1B,

T and X are, independently of each other, O or S,

A is N(Q ₁ )(Q ₂ )(Q ₃ )(Q ₄ ) or a metal,

Ring CY ₁ is a saturated 5-membered ring, a saturated 6-membered ring, a saturated 7-membered ring, or a saturated 8-membered ring,

Y ₁ is C,

Y ₂ is C(R ₀ )(R ₁ ) or N(R ₁ ),

Y ₁ and Y ₂ are connected to each other by a single bond,

R ₀ is *-OH, *-SH, *-C(=O)OH, *-C(=S)OH, *-C(=O)SH, *-C(=S)SH or *-N (Q ₃₁ )(Q ₃₂ ),

R ₁ to R ₄ are independently of each other,

hydrogen;

*-OZ ₁₁ , *-SZ ₁₁ , *-C(=O)OZ ₁₁ , *-C(=S)OZ ₁₁ , *-C(=O)SZ ₁₁ , *-C(=S)SZ ₁₁ or *-N(R ₁₁ )(R ₁₂ ); or

*-OZ ₂₁ , *-SZ ₂₁ , *-C(=O)OZ ₂₁ , *-C(=S)OZ ₂₁ , *-C(=O)SZ ₂₁ , *-C(=S)SZ ₂₁ , *-N(R ₂₁ )(R ₂₂ ), or a C ₁ -C ₂₀ alkyl group substituted or unsubstituted by any combination thereof;

ego,

Z ₁₁ is hydrogen, N(Q ₁₁ )(Q ₁₂ )(Q ₁₃ )(Q ₁₄ ) or a metal,

Z ₂₁ is hydrogen, N(Q ₂₁ )(Q ₂₂ )(Q ₂₃ )(Q ₂₄ ) or a metal,

Q ₁ to Q ₄ , Q ₁₁ to Q ₁₄ , Q ₂₁ to Q ₂₄ , Q ₃₁ , Q ₃₂ , R ₁₁ , R ₁₂ , R ₂₁ and R ₂₂ are each independently selected from hydrogen, C ₁ -C ₂₀ alkyl group or C ₆ -C ₂₀ is an aryl group,

n is 0 or 1,

a1 is an integer from 0 to 10,

* is a bonding site with a neighboring atom.

According to one embodiment, the solvent may include water.

According to another embodiment, in Formula 1A, Y ₂ may be C(R ₀ )(R ₁ ), R ₀ may be *-OH or *-SH, and R ₁ may be hydrogen.

According to another embodiment, in Formula 1A, Y ₂ may be N(R ₁ ) and R ₁ may be hydrogen.

According to another embodiment, at least one of R ₁ to R ₄ in Formula 1B is,

*-C(=O)OZ ₁₁ ; or

*-C(=O)OZ ₂₁ C ₁ -C ₂₀ alkyl group substituted;

ego,

The Z ₁₁ is N(Q ₁₁ )(Q ₁₂ )(Q ₁₃ )(Q ₁₄ ),

The Z ₂₁ may be N(Q ₂₁ )(Q ₂₂ )(Q ₂₃ )(Q ₂₄ ).

According to another embodiment, the cleaning accelerator may include a salt represented by one of the following formulas 1C to 12C or any combination thereof:

In the above formulas 1C to 12C,

A is N(Q ₁ )(Q ₂ )(Q ₃ )(Q ₄ ),

Z is hydrogen or N(Q ₂₁ )(Q ₂₂ )(Q ₂₃ )(Q ₂₄ ),

Q ₁ to Q ₄ and Q ₂₁ to Q ₂₄ are each independently hydrogen, a C ₁ -C ₂₀ alkyl group, or a C ₆ -C ₂₀ aryl group.

According to another embodiment, the content of the cleaning accelerator may be 0.01 wt% to 10 wt% per 100 wt% of the cleaning composition for removing surface residues.

According to another embodiment, the cleaning composition may further include a pH adjuster.

According to another embodiment, the surface residue is a residue created on the surface of the metal-containing film after surface treatment of the metal-containing film and separated from the metal-containing film, and the surface residue is a residue formed on the surface of the metal-containing film. It may contain metals derived from.

According to another embodiment, the anion separated from the cation A ⁺ in Formulas 1A and 1B binds to the metal atom contained in the surface residue, but does not bind to the metal atom contained in the metal-containing film. You can.

According to the other aspect,

Preparing a cleaning composition for removing the surface residue; and

contacting the cleaning composition for removing surface residues with a substrate provided with a metal-containing film on which surface residues are generated;

A method for cleaning a metal-containing film, including a method, is provided.

According to another aspect,

Preparing a cleaning composition for removing the surface residue; and

contacting the cleaning composition for removing surface residues with a substrate provided with a metal-containing film on which surface residues are generated;

A semiconductor device manufacturing method including a semiconductor device is provided.

The cleaning composition has excellent surface residue removal performance and at the same time does not damage the surface of the film to be cleaned. By using it, the surface of the metal-containing film can be effectively cleaned and a high-performance semiconductor device can be manufactured.

cleaning target film

The film to be cleaned may include a metal-containing film.

The metal contained in the metal-containing film is an alkali metal (e.g., sodium (Na), potassium (K), rubidium (Rb), cesium (Cs), etc.), an alkaline earth metal (e.g., beryllium (Be), etc. , magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), etc.), lanthanum group metals (e.g., lanthanum (La), europium (Eu), terbium (Tb), ytterbium (Yb) ), etc.), transition metals (e.g., scandium (Sc), yttrium (Y), titanium (Ti), zirconium (Zr), hafnium (Hf), vanadium (V), niobium (Nb), tantalum ( Ta), chromium (Cr), molybdenum (Mo), tungsten (W), manganese (Mn), iron (Fe), ruthenium (Ru), osmium (Os), cobalt (Co), rhodium (Rh), Nickel (Ni), copper (Cu), silver (Ag), zinc (Zn), etc.), post-transfer metals (e.g. aluminum (Al), gallium (Ga), indium (In), thallium (Tl), tin (Sn), bismuth (Bi), etc.), or any combination thereof.

According to one embodiment, the metal-containing film is indium (In), titanium (Ti), aluminum (Al), copper (Cu), tungsten (W), cobalt (Co), lanthanum (La), scandium (Sc), and gallium. (Ga), zinc (Zn), hafnium (Hf), or any combination thereof.

For example, the metal-containing film may include aluminum, copper, titanium, tungsten, cobalt, or any combination thereof.

As another example, the metal-containing layer may include aluminum.

As another example, the metal-containing film may include titanium.

As another example, the metal-containing film may include titanium and aluminum.

The metal-containing film may include a metal nitride film (or a metal nitride-containing film). The metal-containing film may include, for example, a titanium nitride film (or a titanium nitride-containing film). The titanium nitride film may further include copper, indium, aluminum, lanthanum, scandium, gallium, hafnium, zinc, or any combination thereof.

As another example, the metal-containing film may include a metal oxide film (or a metal oxide-containing film). The metal oxide film may include titanium, copper, aluminum, lanthanum, scandium, gallium, hafnium, or any combination thereof. For example, the metal oxide may include an aluminum oxide film (i.e., an aluminum oxide-containing film), an IGZO (indium gallium zinc oxide)-containing film, etc.

As another example, the metal-containing layer may include the metal nitride layer and the metal oxide layer.

As another example, the metal-containing film includes, in addition to metals, metalloids (e.g., boron (B), silicon (Si), germanium (Ge), arsenic (As), antimony (Sb), and tellurium ( Te), etc.), non-metals (e.g., nitrogen (N), phosphorus (P), oxygen (O), sulfur (S), selenium (Se), etc.), and any combination thereof.

The metal-containing film may have a single-layer structure made of two or more types of materials, or may have a multi-layer structure including different materials. For example, the metal-containing film may have i) a single-layer structure of a titanium nitride film, ii) a double-layer structure including a titanium nitride film further containing aluminum and a titanium nitride film, or iii) a double-layer structure including a titanium nitride film and a silicon nitride film, etc. You can have

Cleaning composition for removing surface residues

The cleaning composition includes a solvent and a cleaning accelerator.

According to one embodiment, the solvent may include water (eg, deionized water).

As another example, the solvent may include alcohol (eg, 2-propanol).

The cleaning accelerator may include a salt represented by Formula 1A below, a salt represented by Formula 1B below, or a combination thereof:

<Formula 1A> <Formula 1B>

In Formulas 1A and 1B, T and X may be independently O or S.

In Formulas 1A and 1B, A may be N(Q ₁ )(Q ₂ )(Q ₃ )(Q ₄ ) or a metal (e.g., Na, Mg, K, Ca, Al, Cu, or Zn, etc.) there is. For example, A may be N(Q ₁ )(Q ₂ )(Q ₃ )(Q ₄ ). The A constitutes a cation in Formulas 1A and 1B. For a description of each of Q ₁ to Q ₄ , refer to what is described herein.

Ring CY ₁ in Formula 1A may be a saturated 5-membered ring, a saturated 6-membered ring, a saturated 7-membered ring, or a saturated 8-membered ring.

For example, the ring CY ₁ may be a saturated 5-membered ring (eg, pyrrolidine) or a saturated 6-membered ring (eg, cyclohexane, piperidine, etc.).

로 표시된 그룹에 대한 α(알파)-탄소이다. In Formulas 1A and 1B, Y ₁ is C. Y ₁ is in formulas 1A and 1B.

is the α (alpha)-carbon for the group indicated.

In Formula 1A, Y ₂ may be C(R ₀ )(R ₁ ) or N(R ₁ ). For descriptions of each of R ₀ and R ₁ , refer to what is described herein.

In Formula 1A, Y ₁ and Y ₂ are connected to each other by a single bond.

In Formulas 1A and 1B, R ₀ is *-OH, *-SH, *-C(=O)OH, *-C(=S)OH, *-C(=O)SH, *-C(=S )SH or *-N(Q ₃₁ )(Q ₃₂ ).

In Formulas 1A and 1B, R ₁ to R ₄ are independently of each other,

hydrogen;

*-OZ ₁₁ , *-SZ ₁₁ , *-C(=O)OZ ₁₁ , *-C(=S)OZ ₁₁ , *-C(=O)SZ ₁₁ , *-C(=S)SZ ₁₁ or *-N(R ₁₁ )(R ₁₂ ); or

*-OZ ₂₁ , *-SZ ₂₁ , *-C(=O)OZ ₂₁ , *-C(=S)OZ ₂₁ , *-C(=O)SZ ₂₁ , *-C(=S)SZ ₂₁ , *-N(R ₂₁ )(R ₂₂ ), or a C ₁ -C ₂₀ alkyl group substituted or unsubstituted by any combination thereof;

It can be. Here, Z ₁₁ is hydrogen, N(Q ₁₁ )(Q ₁₂ )(Q ₁₃ )(Q ₁₄ ), or a metal (e.g., Na, Mg, K, Ca, Al, Cu, or Zn, etc.), and Z ₂₁ may be hydrogen, N(Q ₂₁ )(Q ₂₂ )(Q ₂₃ )(Q ₂₄ ), or a metal (e.g., Na, Mg, K, Ca, Al, Cu, or Zn, etc.).

In the present specification, Q ₁ to Q ₄ , Q ₁₁ to Q ₁₄ , Q ₂₁ to Q ₂₄ , Q ₃₁ , Q ₃₂ , R ₁₁ , R ₁₂ , R ₂₁ and R ₂₂ are each independently hydrogen, C ₁ -C ₂₀ It may be an alkyl group (eg, hydrogen or C ₁ -C ₁₀ alkyl group) or a C ₆ -C ₂₀ aryl group (eg, phenyl group, naphthyl group, etc.).

As another example, in Formulas 1A and 1B, R ₁ to R ₄ are independently hydrogen atom, deuterium atom, halogen atom, cycloalkyl, aryl, heteroaryl, heteroalicyclic, hydroxy, alkoxy, aryloxy. , phosphonic acid, carboxy, mercapto, alkylthio, arylthio, cyano, halogen, carbonyl, thiocarbonyl, O-carbamyl, N-carbamyl, O-thiocarbamyl, N-thiocarbamyl, C -Amido, N-amido, S-sulfonamido, N-sulfonamido, C-carboxy, O-carboxy, isocyanato, thiocyanato, isothiocyanato, nitro, cyryl, tri. It may be selected from the group consisting of halomethanesulfonyl, amino and their derivatives, and combinations thereof are also possible. For example, R ₁ may be -CHF ₂ , which is a combination of a halogen atom and an alkyl group, or -CD ₂ Br , which is a combination of a deuterium atom, an alkyl group, and a halogen atom.

In Formula 1B, n may be 0 or 1. When n is 0, R ₀ is directly connected to Y ₁ .

In Formula 1A, a1 may be an integer from 0 to 10.

In this specification, * refers to a binding site with a neighboring atom, unless otherwise indicated.

According to one embodiment, in Formula 1A,

Y ₂ is C(R ₀ )(R ₁ ),

R ₀ is *-OH or *-SH,

R ₁ may be hydrogen.

According to another embodiment, in Formula 1A,

Y ₂ is N(R ₁ ),

R ₁ may be hydrogen.

According to another embodiment, at least one of R ₁ to R ₄ in Formula 1B is,

*-C(=O)OZ ₁₁ ; or

*-C(=O)OZ ₂₁ C ₁ -C ₂₀ alkyl group substituted;

ego,

The Z ₁₁ is N(Q ₁₁ )(Q ₁₂ )(Q ₁₃ )(Q ₁₄ ),

The Z ₂₁ may be N(Q ₂₁ )(Q ₂₂ )(Q ₂₃ )(Q ₂₄ ).

According to another embodiment, the cleaning accelerator may not include ammonium citrate and ammonium lactate.

According to another embodiment, the cleaning accelerator may include a salt represented by one of the following formulas 1C to 12C or any combination thereof:

In the above formulas 1C to 12C,

A is N(Q ₁ )(Q ₂ )(Q ₃ )(Q ₄ ),

Z is hydrogen or N(Q ₂₁ )(Q ₂₂ )(Q ₂₃ )(Q ₂₄ ),

Q ₁ to Q ₄ and Q ₂₁ to Q ₂₄ are each independently hydrogen, a C ₁ -C ₂₀ alkyl group, or a C ₆ -C ₂₀ aryl group.

According to another embodiment, the cleaning accelerator may not include a salt represented by Formula 5C, a salt represented by Formula 7C, and a salt represented by Formula 10C.

The content of the cleaning accelerator may be 0.01 wt% to 10 wt%, 0.01 wt% to 5 wt%, or 0.5 wt% to 2 wt% per 100 wt% of the cleaning composition for removing surface residues. When the content of the cleaning accelerator satisfies the above-mentioned range, surface residues can be effectively removed and damage to the surface of the film being cleaned can be minimized.

The cleaning composition may further include a pH adjuster in addition to a solvent and a cleaning accelerator. The pH adjusting agent may include, for example, ammonium hydroxide, ammonium hydroxide substituted with at least one C ₁ -C ₂₀ alkyl group, or any combination thereof.

The content of the pH adjuster may be 0.01 wt% to 10 wt%, 0.01 wt% to 5 wt%, or 0.5 wt% to 2 wt% per 100 wt% of the cleaning composition for removing surface residues. When the content of the pH adjuster satisfies the range described above, the pH of the cleaning composition can be maintained at an appropriate level. For example, the cleaning composition can have a pH of 8 or less.

The cleaning composition may contain no oxidizing agent, fluorine-containing compound, or organic solvent. The oxidizing agent may cause damage to the surface of the film being cleaned during cleaning, and the fluorine-containing compound and organic solvent may interfere with pH control of the cleaning composition.

According to one embodiment, the cleaning accelerator may consist of a salt represented by Formula 1A, a salt represented by Formula 1B, or a combination thereof.

The surface residue to be removed with the cleaning composition described in this specification refers to the film to be cleaned, for example, a metal-containing film, which is separated from the metal-containing film after surface treatment (for example, dry etching treatment, etc.). It may be a residue generated on the surface of the metal-containing film.

According to one embodiment, the surface residue may include a metal (eg, aluminum, copper, titanium, tungsten, cobalt, or any combination thereof) derived from the metal-containing film.

According to another embodiment, the metal-containing film may include aluminum, copper, titanium, tungsten, cobalt, or any combination thereof.

The anion separated from the cation A ⁺ in Formulas 1A and 1B combines with an atom included in the surface residue, for example, a metal atom (e.g., a titanium atom, an aluminum atom, a copper atom, etc.), and It does not substantially bond with atoms included in the film to be cleaned, for example, a metal-containing film, for example, with metal atoms. Accordingly, the cleaning composition of the present specification is clearly distinguished from an “etching” composition that removes atoms included in the target film, for example, atoms included in the target film by being bonded to each other through chemical bonds.

For example, each of Y ₂ in Formula 1A and R ₀ in Formula ^1B , together with By forming a 5- or 6-membered cyclometalated ring, the metal atoms contained in the residue can be effectively hydrated. As a result, damage to the surface of the metal-containing film, which is the film to be cleaned, is minimized, and at the same time, surface residues can be effectively removed.

Additionally, A constituting the cation in Formulas 1A and 1B may be N(Q ₁ )(Q ₂ )(Q ₃ )(Q ₄ ) or a metal. That is, A ⁺ in the above formulas 1A and 1B is not H ⁺ , and as a result, the reaction rate with metal atoms contained in the surface residue can be increased to obtain an excellent cleaning effect.

Metal-containing film cleaning method and semiconductor device manufacturing method

The metal-containing film cleaning method and semiconductor device manufacturing method are,

preparing a cleaning composition for removing surface residues as described herein; and

contacting the cleaning composition for removing surface residues with a substrate provided with a metal-containing film on which surface residues are generated;

may include.

For descriptions of the surface residues and metal-containing films, refer to those described herein.

Upon contact between the cleaning composition for removing surface residues and a substrate provided with a metal-containing film on which the surface residues are generated, the anions separated from the cations A ⁺ in Formulas 1A and 1B are converted to metal atoms contained in the surface residues. and may not bond with metal atoms included in the metal-containing film.

Meanwhile, the metal-containing film cleaning method and the semiconductor device manufacturing method further include rinsing the substrate provided with the metal-containing film with an additional solvent, and optionally, drying the substrate provided with the metal-containing film to remove the additional solvent. Additional steps may be included.

Examples 1 to 3 and Comparative Examples 1 to 6

The cleaning compositions of Examples 1 to 3 and Comparative Examples 1 to 6 were prepared by mixing the solvent, cleaning accelerator (1 wt%), pH adjuster (1 wt%) and/or oxidizing agent (10 wt% to 20 wt%) as shown in Table 1. Manufactured. Deionized water was used as the solvent, and the solvent content corresponds to the balance per 100 wt% of the cleaning composition. Each of the prepared cleaning compositions was placed in a beaker and heated to 70°C, then the titanium/aluminum nitride film on which the plasma etching treatment was performed was immersed in each cleaning composition for 5 minutes, and an ellipse measuring device, a sheet resistance meter, and an XRF (X-ray fluorescence) were used. ) equipment and XRR (X-ray reflectometry) equipment were used to evaluate the film etch rate during immersion, and the results are shown in Table 1. Next, the titanium/aluminum nitride film was taken out, rinsed with deionized water, and dried under a nitrogen atmosphere. Then, the surface residue cleaning power was evaluated by checking whether surface residue remained on the film surface using a TEM (Transmission Electron Microscope) equipment. is shown in Table 1. The titanium/aluminum nitride film refers to a titanium nitride-containing film that further contains aluminum.

sejung
accelerant pH regulator oxidizing agent surface residue
Cleansing power Etch rate of titanium/aluminum nitride film
(Å/min) Example 1 One - - O < 5 Example 2 2 - - O < 5 Example 3 3 ammonium hydroxide - O < 5 Comparative Example 1 A - - △ < 5 Comparative Example 2 B - - △ < 5 Comparative Example 3 C - - X < 5 Comparative Example 4 D - - △ < 5 Comparative Example 5 One - H ₂ O ₂ O 75 Comparative Example 6 A - H ₂ O ₂ O 90

Surface residue cleaning power O: All surface residues are removed under the cleaning conditions.

Surface residue cleaning power △: A small amount of surface residue was removed under the cleaning conditions.

Surface residue cleaning power

From Table 1, the cleaning compositions of Comparative Examples 1 to 4 do not substantially damage the surface of the target film under the cleaning conditions, but have poor cleaning power, and the cleaning compositions of Comparative Examples 5 and 6 have excellent cleaning power, but have poor cleaning power under the cleaning conditions. It was confirmed that the membrane surface was damaged. On the other hand, it was confirmed that the cleaning compositions of Examples 1 to 3 had excellent cleaning power without substantially damaging the surface of the target film under the cleaning conditions.

Claims (20)

Contains a solvent and a cleaning accelerator,
Contains no oxidizing agent,
The cleaning accelerator is a cleaning composition for removing residues on surfaces, comprising a salt represented by Formula 1A below, a salt represented by Formula 1B below, or a combination thereof:
<Formula 1A><Formula1B>

In formulas 1A and 1B,
T and X are, independently of each other, O or S,
A is N(Q ₁ )(Q ₂ )(Q ₃ )(Q ₄ ) or a metal,
Ring CY ₁ is a saturated 5-membered ring, a saturated 6-membered ring, a saturated 7-membered ring, or a saturated 8-membered ring,
Y ₁ is C,
Y ₂ is C(R ₀ )(R ₁ ) or N(R ₁ ),
Y ₁ and Y ₂ are connected to each other by a single bond,
R ₀ is *-OH, *-SH, *-C(=O)OH, *-C(=S)OH, *-C(=O)SH, *-C(=S)SH or *-N (Q ₃₁ )(Q ₃₂ ),
R ₁ to R ₄ are independently of each other,
hydrogen;
*-OZ ₁₁ , *-SZ ₁₁ , *-C(=O)OZ ₁₁ , *-C(=S)OZ ₁₁ , *-C(=O)SZ ₁₁ , *-C(=S)SZ ₁₁ or *-N(R ₁₁ )(R ₁₂ ); or
*-OZ ₂₁ , *-SZ ₂₁ , *-C(=O)OZ ₂₁ , *-C(=S)OZ ₂₁ , *-C(=O)SZ ₂₁ , *-C(=S)SZ ₂₁ , *-N(R ₂₁ )(R ₂₂ ), or a C ₁ -C ₂₀ alkyl group substituted or unsubstituted by any combination thereof;
ego,
Z ₁₁ is hydrogen, N(Q ₁₁ )(Q ₁₂ )(Q ₁₃ )(Q ₁₄ ) or a metal,
Z ₂₁ is hydrogen, N(Q ₂₁ )(Q ₂₂ )(Q ₂₃ )(Q ₂₄ ) or a metal,
Q ₁ to Q ₄ , Q ₁₁ to Q ₁₄ , Q ₂₁ to Q ₂₄ , Q ₃₁ , Q ₃₂ , R ₁₁ , R ₁₂ , R ₂₁ and R ₂₂ are each independently selected from hydrogen, C ₁ -C ₂₀ alkyl group or C ₆ -C ₂₀ is an aryl group,
n is 0 or 1,
a1 is an integer from 0 to 10,
* is a bonding site with a neighboring atom. According to paragraph 1,
A cleaning composition for removing surface residues, wherein the solvent includes water. According to paragraph 1,
In Formula 1B, n is 0, a cleaning composition for removing surface residues. According to paragraph 1,
In Formula 1A,
Y ₂ is C(R ₀ )(R ₁ ),
R ₀ is *-OH or *-SH,
R ₁ is hydrogen. A cleaning composition for removing surface residues. According to paragraph 1,
In Formula 1A,
Y ₂ is N(R ₁ ),
R ₁ is hydrogen. A cleaning composition for removing surface residues. According to paragraph 1,
At least one of R ₁ to R ₄ in Formula 1B is,
*-C(=O)OZ ₁₁ ; or
*-C(=O)OZ ₂₁ C ₁ -C ₂₀ alkyl group substituted;
ego,
The Z ₁₁ is N(Q ₁₁ )(Q ₁₂ )(Q ₁₃ )(Q ₁₄ ),
Wherein Z ₂₁ is N(Q ₂₁ )(Q ₂₂ )(Q ₂₃ )(Q ₂₄ ). According to paragraph 1,
A cleaning composition for removing surface residues, wherein the cleaning accelerator comprises a salt represented by one of the formulas 1C to 12C or any combination thereof:

In the above formulas 1C to 12C,
A is N(Q ₁ )(Q ₂ )(Q ₃ )(Q ₄ ),
Z is hydrogen or N(Q ₂₁ )(Q ₂₂ )(Q ₂₃ )(Q ₂₄ ),
Q ₁ to Q ₄ and Q ₂₁ to Q ₂₄ are each independently hydrogen, a C ₁ -C ₂₀ alkyl group, or a C ₆ -C ₂₀ aryl group. According to paragraph 1,
A cleaning composition for removing surface residues, wherein the content of the cleaning accelerator is 0.01 wt% to 10 wt% per 100 wt% of the cleaning composition for removing surface residues. According to paragraph 1,
A cleaning composition for removing surface residues, further comprising a pH adjusting agent. According to paragraph 1,
A cleaning composition for removing surface residues, having a pH of less than 8. According to paragraph 1,
A cleaning composition for removing surface residues, free of fluorine-containing compounds and organic solvents. According to paragraph 1,
A cleaning composition for removing surface residues, wherein the cleaning accelerator consists of a salt represented by Formula 1A, a salt represented by Formula 1B, or a combination thereof. According to paragraph 1,
The surface residue is a residue created on the surface of the metal-containing film and separated from the metal-containing film after surface treatment of the metal-containing film,
A cleaning composition for removing surface residues, wherein the surface residues include metal derived from the metal-containing film. According to clause 13,
A cleaning composition for removing surface residues, wherein the metal-containing film includes aluminum, copper, titanium, tungsten, cobalt, or any combination thereof. According to clause 13,
Cleaning for removing surface residues in which the anion separated from the cation A ⁺ in the formulas 1A and 1B binds to the metal atom contained in the surface residue but does not bind to the metal atom contained in the metal-containing film. Composition. Preparing a cleaning composition for removing surface residues according to any one of claims 1 to 15; and
contacting the cleaning composition for removing surface residues with a substrate provided with a metal-containing film on which surface residues are generated;
Including, a method of cleaning a metal-containing film. According to clause 16,
The surface residue is a residue created on the surface of the metal-containing film and separated from the metal-containing film after surface treatment of the metal-containing film,
The surface residue includes metal derived from the metal-containing film,
When the cleaning composition for removing surface residues comes in contact with a substrate provided with a metal-containing film on which the surface residues are generated, the anions separated from the cations A ⁺ in Formulas 1A and 1B are separated from the metal atoms contained in the surface residues. A method of cleaning a metal-containing film, wherein the metal-containing film binds to and does not bond to the metal atoms contained in the metal-containing film. According to clause 16,
A method of cleaning a metal-containing film, wherein the metal-containing film includes aluminum, copper, titanium, tungsten, cobalt, or any combination thereof. According to clause 16,
Further comprising rinsing the substrate provided with the metal-containing film with an additional solvent,
Optionally, the method of cleaning a metal-containing film further includes drying the substrate provided with the metal-containing film to remove the additional solvent. Preparing a cleaning composition for removing surface residues according to any one of claims 1 to 15; and
contacting the cleaning composition for removing surface residues with a substrate provided with a metal-containing film on which surface residues are generated;
Including, semiconductor device manufacturing method.