Patent Application
20230383218
This application claims priority to Korean Patent Applications Nos. 10-2022-0065552, filed on May 27, 2022, 10-2022-0121142, filed on Sep. 23, 2022, and 10-2023-0067189, filed on May 24, 2023, in the Korean Intellectual Property Office, and all the benefits accruing therefrom under 35 U.S.C. § 119, the contents of which are incorporated by reference herein in their entireties.
The disclosure relates to a cleaning composition for removing residues on surfaces, a method of cleaning a metal-containing film by using the same, and a method of manufacturing a semiconductor device by using the same.
To satisfy requests of consumers for semiconductor devices, i.e., excellent performance and low price, an increase in the degree of integration and improvement in reliability of semiconductor devices are desired. As the degree of integration of the semiconductor devices increases, damage to components of the semiconductor devices has a greater effect on the reliability and electrical characteristics of semiconductor devices during a manufacturing process thereof. In particular, in the manufacturing process of the semiconductor devices, surface residues generated as a result of surface treatment (e.g., dry etching, etc.) on a predetermined film (e.g., a metal-containing film) may cause exfoliation of a film, which is additionally laminated, or generation of cracks. In addition, various chemical substances may be absorbed or adsorbed on the surface residues through moisture, causing a phenomenon in which a film existing around the surface residues is additionally etched. Therefore, there is a continuing need for an effective cleaning composition and process, which can remove substantially all of the surface residues, and at the same time, does not cause defects in products including a metal-containing film without damaging the surface of a target film to be cleaned.
Provided are a cleaning composition, which can provide excellent detergency, and at the same time, does not damage a target film to be cleaned, a method of cleaning a metal-containing film by using the same, and a method of manufacturing a semiconductor device by using the same.
Additional aspects will be set forth in part in the description which follows and, in part, will be apparent from the description, or may be learned by practice of the presented embodiments of the disclosure.
According to an aspect of the disclosure, a cleaning composition for removing residues on surfaces includes:
In Formulae 1A and 1B,
The solvent in the cleaning composition for removing residues on surfaces may include water.
In Formula 1B, n may be 0.
In Formula 1A, Y2 may be C(R0)(R1), R0 may be *—OH or *—SH, and R1 may be hydrogen.
In Formula 1A, Y2 may be N(R1), and R1 may be hydrogen.
In Formula 1B, at least one of R1 to R4 may be
In Formula 1B, n may be 0, and R0 may be *—OH, *—SH, or *—NH2.
In Formula 1B, R1 may be hydrogen.
In Formula 1B, R2 may be hydrogen; a unsubstituted C1C5 alkyl group; or a C1-C5 alkyl group substituted with *—OH, *—SH, *—C(═O)—O(Z21), *—C(═O)—O—(Z22)+, *—NH2, or any combination thereof.
The cleaning accelerator may further include at least one of a compound represented by Formula 1A(1), a compound represented by Formula 1B(1), a compound represented by Formula 1P-1, or a compound represented by Formula 1P-2:
An amount of the cleaning accelerator may be, per 100 wt % of the cleaning composition for removing residues on surfaces, in a range of about 0.01 wt % to about 10 wt %.
The cleaning composition for removing residues on surfaces may further include a pH adjuster.
The cleaning composition for removing residues may not include a fluorine-containing compound and an organic solvent.
The residues on surfaces may be, after a metal-containing film is surface-treated, separated from the metal-containing film and generated on the surface of the metal-containing film, and in this regard, may include a metal derived from the metal-containing film.
The metal-containing film may include aluminum, copper, titanium, tungsten, cobalt, or any combination thereof.
In the cleaning composition for removing residues on surfaces, at least one of an anion represented by Formula 1A(2) or an anion represented by Formula 1B(2) may be linked to a metal atom included in the residues on surfaces, and may not be linked to a metal atom included in the metal-containing film:
wherein, T, X, ring CY1, Y2, R0 to R4, n, and a1 in Formulae 1A(2) and 1B(2) are each the same as described herein, Y1 in Formula 1A(2) is the same as described in connection with Y1 in Formula 1A described herein, and Y1 in Formula 1B(2) is carbon.
According to another aspect of the disclosure, a method of cleaning a metal-containing film includes:
The preparing of the cleaning composition for removing residues on surfaces may include preparing the cleaning accelerator by mixing at least one of the compound represented by Formula 1A(1) or the compound represented by Formula 1B(1) with at least one of the compound represented by Formula 1P-1 or the compound represented by Formula 1P-2. Formulae 1A(1), 1B(1), 1P-1 and 1P-2 are the same as described above.
According to another aspect of the disclosure, a method of manufacturing a semiconductor includes:
Reference will now be made in detail to embodiments, examples of which are illustrated in the accompanying drawings, wherein like reference numerals refer to like elements throughout. In this regard, the present embodiments may have different forms and should not be construed as being limited to the descriptions set forth herein. Accordingly, the embodiments are merely described below, by referring to the FIGURE, to explain aspects. As used herein, the term “and/or” includes any and all combinations of one or more of the associated listed items. Expressions such as “at least one of,” when preceding a list of elements, modify the entire list of elements and do not modify the individual elements of the list.
It will be understood that when an element is referred to as being “on” another element, it can be directly on the other element or intervening elements may be present therebetween. In contrast, when an element is referred to as being “directly on” another element, there are no intervening elements present.
The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting. As used herein, “a”, “an,” “the,” and “at least one” do not denote a limitation of quantity, and are intended to include both the singular and plural, unless the context clearly indicates otherwise. For example, “an element” has the same meaning as “at least one element,” unless the context clearly indicates otherwise. It will be further understood that the terms “comprises” and/or “comprising,” or “includes” and/or “including” when used in this specification, specify the presence of stated features, regions, integers, steps, operations, elements, and/or components, but do not preclude the presence or addition of one or more other features, regions, integers, steps, operations, elements, components, and/or groups thereof.
“About” or “approximately” as used herein is inclusive of the stated value and means within an acceptable range of deviation for the particular value as determined by one of ordinary skill in the art, considering the measurement in question and the error associated with measurement of the particular quantity (i.e., the limitations of the measurement system). For example, “about” can mean within one or more standard deviations, or within ±30%, 20%, 10% or 5% of the stated value.
Unless otherwise defined, all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure belongs. It will be further understood that terms, such as those defined in commonly used dictionaries, should be interpreted as having a meaning that is consistent with their meaning in the context of the relevant art and the present disclosure, and will not be interpreted in an idealized or overly formal sense unless expressly so defined herein.
A target film to be cleaned may include a metal-containing film.
A metal included in the metal-containing film may include an alkali metal (e.g., sodium (Na), potassium (K), rubidium (Rb), cesium (Cs), etc.), an alkaline earth metal (e.g., beryllium (Be), magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), etc.), a lanthanide metal (e.g., lanthanum (La), europium (Eu), terbium (Tb), ytterbium (Yb), etc.), a transition metal (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.), a post-transition metal (e.g., aluminum (AI), gallium (Ga), indium (In), thallium (TI), tin (Sn), bismuth (Bi), etc.), or any combination thereof.
In an embodiment, the metal-containing film may include In, Ti, Al, Cu, W, Co, La, Sc, Ga, Zn, Hf, or any combination thereof.
In one or more embodiments, the metal-containing film may include Al, Cu, Ti, W, Co, or any combination thereof.
In one or more embodiments, the metal-containing film may include Al.
In one or more embodiments, the metal-containing film may include Ti.
In one or more embodiments, the metal-containing film may include Ti and Al.
In one or more embodiments, the metal-containing film may include a metal nitride-containing film (e.g., a metal nitride film). In one or more embodiments, the metal-containing film may include a titanium nitride-containing film (e.g., a titanium nitride film).
The titanium nitride-containing film may further include Cu, In, Al, La, Sc, Ga, Hf, Zn, or any combination thereof.
In one or more embodiments, the metal-containing film may include a metal oxide-containing film (e.g., a metal oxide film). The metal oxide-containing film may include Ti, Cu, Al, La, Sc, Ga, Hf, or any combination thereof. For example, the metal oxide-containing film may include an aluminum oxide-containing film (e.g., an aluminum oxide film), an indium gallium zinc oxide (IGZO)-containing film, and the like.
In one or more embodiments, the metal-containing film may include the metal nitride-containing film and the metal oxide-containing film.
In one or more embodiments, the metal-containing film may further include, in addition to the aforementioned metal, a metalloid (e.g., boron (B), silicon (Si), germanium (Ge), arsenic (As), antimony (Sb), tellurium (Te), etc.), a non-metal(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 consisting of two or more types of materials or a multi-layer structure including different materials for each layer. For example, the metal-containing film may have i) a single-layer structure consisting of a titanium nitride-containing film (e.g., a titanium nitride film), ii) a double-layer structure consisting of a titanium nitride-containing film, which further includes Al, and a titanium nitride film, or iii) a double-layer structure consisting of a titanium nitride film and a silicon nitride film.
A cleaning composition may include a solvent and a cleaning accelerator.
In an embodiment, the solvent may include water (e.g., deionized water).
In one or more embodiments, the solvent may include an alcohol (e.g., 2-propanol), optionally in combination with water.
The cleaning accelerator includes at least one of a salt represented by Formula 1A or a salt represented by Formula 1B:
In Formulae 1A and 1B, T and X are independently be O or S.
In Formulae 1A and 1B, A is N(Q1)(Q2)(Q3)(Q4) or a metal (e.g., Na, K, Rb, Cs, etc.). For example, A may be N(Q1)(Q2)(Q3)(Q4). A may constitute a cation in Formulae 1A and 1B. Q1 to Q4 are each the same as described in the present specification.
In Formula 1A, ring CY1 is a saturated 5-membered ring, a saturated 6-membered ring, a saturated 7-membered ring, or a saturated 8-membered ring.
For example, ring CY1 may be a saturated 5-membered ring (e.g., pyrrolidine) or a saturated 6-membered ring (e.g., cyclohexane, piperidine, etc.).
In Formula 1A, Y1 is C(R1), and in Formula 1B, Y1 is carbon (C). Carbon of Y1 may be alpha (α)—C with respect to a group represented by
In Formula 1A, Y2 is C(R0)(R1) or N(R1). R0 and R1 are each the same as described in the present specification.
In Formula 1A, Y1 and Y2 are linked to each other via a single bond.
In Formulae 1A and 1B, R0 is *—OH, *—SH, *—C(═O)—OH, *—C(═S)—OH, *—C(═O)—SH, *—C(═S)—SH, or *—N(Q31)(Q32).
In Formulae 1A and 1B, R1 to R4 are each independently:
Here, each of Z11 and Z21 may be hydrogen, Z12 is hydrogen, N(Q11)(Q12)(Q13)(Q14), or a metal (e.g., Na, K, Rb, Cs, etc.), and Z22 is hydrogen, N(Q21)(Q22)(Q23)(Q24), or a metal (e.g., Na, K, Rb, Cs, etc.).
In the present specification, Q1 to Q4, Q11 to Q14, Q21 to Q24, Q31, Q32, R11, R12, R21, and R22 are each independently hydrogen, *—[C(R31)(R32)]m—(R33), or a C6-C20 aryl group.
In *—[C(R31)(R32)]m—(R33), R31 to R33 may each independently be:
In *—[C(R31)(R32)]m—(R33), m indicates numbers of a group represented by *—C(R31)(R32)—*′ and may be an integer from 1 to 30, an integer from 1 to 20, an integer from 1 to 20, or an integer from 1 to 5. When m is 2 or greater, two or more of a group represented by *—C(R31)(R32)—*′ may be identical to or different from each other.
At least one *—C(R31)(R32)—*′ included in *—[C(R31)(R32)]m—(R33) may be optionally substituted with *—O—*′, *—S—*′ or *—N(R31)—*′. R31 of *—N(R31)—*′ is the same as described herein.
Q41, Q42, Q51 and Q52 may each independently be hydrogen, a C1-C20 alkyl group (e.g., a C1-C10 alkyl group or C1-C5 alkyl group), or a C6-C20 aryl group (e.g., a phenyl group, a naphthyl group, etc.).
In one or more embodiments, Q1 to Q4, Q11 to Q14, Q21 to Q24, Q31, Q32, R11, R12, R21, and R22 may each be hydrogen.
In one or more embodiments, at least one of Q1 to Q3, at least one of Q11 to Q13, or at least one of Q21 to Q23 may each be *—[C(R31)(R32)]m—(R33).
In one or more embodiments, in *—[C(R31)(R32)]m—(R33), m may be 5, one *—C(R31)(R32)—*′ among five *—C(R31)(R32)—*'s may be substituted with *—-*′, each of R31 and R32 may be hydrogen, and R33 may be *—OH. For example, *—[C(R31)(R32)]m—(R33) may be *—CH2CH2OCH2CH2OH as shown in Compound 2a described below.
In one or more embodiments, in *—[C(R31)(R32)]m—(R33), m may be an integer from 1 to 5, each of R31 and R32 may be hydrogen, and R33 may be *—NH2. For example, *—[C(R31)(R32)]m—(R33) may be *—CH2CH2NH2 as shown in Compound 2b described below.
In Formula 1B, n is 0 or 1. When n is 0, R0 may be directly linked to Y1.
In Formula 1A, a1 is an integer from 0 to 10, for example, an integer from 0 to 8 or an integer from 0 to 6.
In the present specification, each of * and *′ indicates a binding site to a neighboring atom, unless otherwise indicated.
In an embodiment, in Formula 1A,
In one or more embodiments, in Formula 1A,
In one or more embodiments, at least one of R1 to R4 in Formula 1B may be:
In one or more embodiments, in Formula 1B,
In one or more embodiments, in Formula 1B, R1 may be hydrogen.
In one or more embodiments, in Formula 1B, R2 may be hydrogen; a unsubstituted C1-C5 alkyl group; or a C1-C5 alkyl group substituted with *—OH, *—SH, *—C(═O)—O(Z21), *—C(═O)—O−(Z22)+, *—NH2, or any combination thereof.
The variable definitions as described herein can be combined in any combination that results in a stable compound.
In one or more embodiments, the cleaning accelerator may not include ammonium citrate or ammonium lactate.
In one or more embodiments, the cleaning accelerator may further include at least one of a compound represented by Formula 1A(1), a compound represented by Formula 1B(1), a compound represented by Formula 1P-1, or a compound represented by Formula 1P-2:
The compound represented by Formula 1A(1), the compound represented by Formula 11B(1), the compound represented by Formula 1P-1, and the compound represented by Formula 1P-2 may be unreacted compounds at the time of preparing the cleaning accelerator, which will be described below.
The compound represented by Formula 1P-1 may be NH4OH, NaOH, KOH, etc.
The compound represented by Formula 1P-2 may be diglycolamine (NH2CH2CH2OCH2CH2OH), ethylenediamine (NH2CH2CH2NH2), etc.
In one or more embodiments, the cleaning accelerator may include at least one of salts represented by Formulae 1C to 13C:
In Formulae 1C to 13C,
In one or more embodiments, the cleaning accelerator may not include a salt represented by Formula 5C, a salt represented by Formula 7C, or a salt represented by Formula 10C.
In one or more embodiments, the cleaning accelerator may further include at least one of compounds represented by Formulae 1 D to 13D:
wherein X in Formulae 1 D to 13D is the same as described in the present specification.
An amount of the cleaning accelerator may be, per 100 wt % of the cleaning composition for removing residues on surfaces, in a range of about 0.01 wt % to about 10 wt %, about 0.01 wt % to about 5 wt %, or about 0.5 wt % to about 2 wt %. When the amount of the cleaning accelerator is within the ranges above, the residues on surfaces may be effectively removed and damage to the surface of a target film to be cleaned may be also minimized.
The cleaning composition may further include a pH adjuster in addition to the solvent and the cleaning accelerator. The pH adjuster may include, for example ammonium hydroxide (NH4OH), ammonium hydroxide substituted with at least one C1-C20 alkyl group, or any combination thereof.
An amount of the pH adjuster may be, per 100 wt % of the cleaning composition for removing residues on surfaces, in a range of about 0.01 wt % to about 10 wt %, about 0.01 wt % to about 5 wt %, or about 0.5 wt % to about 2 wt %. When the amount of the pH adjuster is satisfied with the ranges above, the pH of the cleaning composition may be maintained at an appropriate level. For example, the cleaning composition may have a pH of 8 or less, for example, a pH from 1 to 8.
The cleaning composition may not include an oxidant, a fluorine-containing compound, or an organic solvent. The oxidant may damage the surface of a target film to be cleaned during cleaning, and the fluorine-containing compound and the organic solvent may interfere with the pH control of the cleaning composition.
In an embodiment, the cleaning accelerator may include (or consists essentially, or consists of) the salt represented by Formula 1A.
In one or more embodiments, the cleaning accelerator may include (or consists essentially of, or consists of):
In one or more embodiments, the cleaning accelerator may include (or consists essentially of, or consists of) the salt represented by Formula 1B.
In one or more embodiments, the cleaning accelerator may include (or consists essentially of or consists of):
In one or more embodiments, the cleaning accelerator may include (or consists essentially of, or consists of) the salt represented by Formula 1A and the salt represented by Formula 1B.
In one or more embodiments, the cleaning accelerator may include (or consists essentially of, or consists of):
The residues on surfaces to be removed by the cleaning composition described in the present specification may refer to, after a target film to be cleaned, e.g., a metal-containing film, is surface-treated (e.g., dry etching-treated), residues separated from the metal-containing film and generated on the surface of the metal-containing film.
In an embodiment, the residues on surfaces may include a metal derived from the metal-containing film (e.g., Al, Cu, Ti, W, Co, or any combination thereof).
In one or more embodiments, the metal-containing film may include Al, Cu, Ti, W, Co, or any combination thereof.
In the cleaning composition for removing residues on surfaces, at least one of an anion represented by Formula 1A(2) or an anion represented by Formula 1B(2) may be linked to an atom e.g., a metal atom (e.g., a titanium atom, an aluminum atom, a copper atom, etc.) included in the residues on surfaces, and may not be linked to an atom, e.g., a metal atom, included in a target film to be cleaned, e.g., the metal-containing film:
wherein, T, X, ring CY1, Y2, R0 to R4, n, and a1 in Formulae 1A(2) and 1B(2) are each the same as described herein, Y1 in Formula 1A(2) is the same as described in connection with Y1 in Formula 1A described herein, and Y1 in Formula 1B(2) is carbon.
Therefore, the cleaning composition described in the present specification is clearly distinguished from an “etching” composition that removes atoms included in a target film, for example, atoms that are linked to each other via chemical bonds and included in a target film.
For example, each of Y2 in Formula 1A and R0 in Formula 1B may be linked to, together with X− in Formulae 1A and 1B, a metal atom included in the residues on surfaces rather than a metal atom included in the metal-containing film, so as to form a 5-membered cyclometallated ring or a 6-membered cyclometallated ring. In this regard, the metal atom included in the residues on surfaces may be effectively bound such as hydrated or the like. Accordingly, damage to the surface of the metal-containing film which is a target film to be cleaned may be minimized, and at the same time, the residues on surfaces may be effectively removed.
In addition, A constituting the cation in Formulae 1A and 1B may be N(Q1)(Q2)(Q3)(Q4) or a metal. That is, A+ in Formulae 1A and 1B is not H+ so that a reaction rate with a metal atom included in the residues on surfaces may be increased to obtain an excellent cleaning effect.
Method of cleaning metal-containing film and method of manufacturing semiconductor device
A method of cleaning the metal-containing film may include:
A method of manufacturing a semiconductor device may include:
The residues on surfaces and the metal-containing film are each the same as described in the present specification.
In an embodiment, the preparing of the cleaning composition for removing residues on surfaces may include preparing the cleaning accelerator by mixing at least one of the compound represented by Formula 1A(1) or the compound represented by Formula 1B(1) with at least one of the compound represented by Formula 1P-1 or the compound represented by Formula 1P-2. When the compound represented by Formula P-2 is used in the preparing of the cleaning composition for removing residues on surfaces, A in Formulae 1A and 1B may be N(Q1)(Q2)(Q3)(Q4) and Q4 in the N(Q1)(Q2)(Q3)(Q4) may be hydrogen.
In an embodiment, the compound represented by Formula 1A(1) may be mixed with the compound represented by Formula 1P-1 (for example, NH4OH) to prepare a cleaning accelerator including the salt represented by Formula 1A, and then, the cleaning accelerator may be mixed with the aforementioned solvent or the like to prepare a cleaning composition for removing residues on surfaces. Here, the cleaning accelerator may further include, as an unreacted reactant, at least one of the compound represented by Formula 1A(1) or the compound represented by Formula 1P-1.
In an embodiment, the compound represented by Formula 1A(1) may be mixed with the compound represented by Formula 1P-2 (for example, NH2CH2CH2OCH2CH2OH, NH2CH2CH2NH2) to prepare a cleaning accelerator including the salt represented by Formula 1A, and then, the cleaning accelerator may be mixed with the aforementioned solvent or the like to prepare a cleaning composition for removing residues on surfaces.
Here, the cleaning accelerator may further include, as an unreacted reactant, at least one of the compound represented by Formula 1A(1) and the compound represented by Formula 1P-2.
In one or more embodiments, the compound represented by Formula 1B(1) (for example, Compound 2′) may be mixed with the compound represented by Formula 1P-1 (for example, NH4OH) to prepare a cleaning accelerator including the salt represented by Formula 1B (for example, Compound 2), and then, the cleaning accelerator may be mixed with the aforementioned solvent or the like to prepare a cleaning composition for removing residues on surfaces. Here, the cleaning accelerator may further include, as an unreacted reactant, at least one of the compound represented by Formula 1B(1) or the compound represented by Formula 1P-1.
In one or more embodiments, the compound represented by Formula 1B(1) (for example, Compound 2′) may be mixed with the compound represented by Formula 1P-2 (for example, NH2CH2CH2OCH2CH2OH or NH2CH2CH2NH2) to prepare a cleaning accelerator including the salt represented by Formula 1B (for example, Compound 2a or Compound 2b), and then, the cleaning accelerator may be mixed with the aforementioned solvent or the like to prepare a cleaning composition for removing residues on surfaces. Here, the cleaning accelerator may further include, as an unreacted reactant, at least one of the compound represented by Formula 11B(1) and the compound represented by Formula 1P-2.
When the cleaning composition for removing residues on surfaces is brought into contact with the metal-containing film provided on a substrate, the metal-containing film having a surface on which residues are generated, at least one of the anion represented by Formula 1A(2) or the anion represented by Formula 1B(2) may be linked to a metal atom included in the residues on surfaces, and may not be linked to a metal atom included in the metal-containing film.
Meanwhile, the method of cleaning the metal-containing film and the method of manufacturing the semiconductor device may further include washing the metal-containing film provided on the substrate using an additional solvent, and may optionally further include removing the additional solvent by drying the metal-containing film, and optionally the substrate.
A solvent was mixed with a cleaning accelerator (1 wt %) and a pH adjuster (1 wt %), and/or an oxidant (20 wt %), if present, shown in Table 1 to prepare cleaning compositions of Examples 1 to 3 and Comparative Examples 1 to 6. Here, deionized water was used as the solvent, and an amount of the solvent corresponds to the remainder per 100 wt % of the cleaning composition. Commercially available Compounds 1 to 3 and A to D were used as the cleaning accelerators.
Each of the prepared cleaning compositions was placed in a beaker and heated until the temperature raised to 70° C., and a plasma-etched titanium/aluminum nitride film was immersed in each of the resulting cleaning compositions for 5 minutes. Then, an ellipsometer, a sheet resistance meter, an X-ray fluorescence (XRF) apparatus, and an X-ray reflectometry (XRR) apparatus were used to evaluate an etching speed during the immersion, and results thereof are shown in Table 1. Next, the titanium/aluminum nitride film was taken out, cleaned with deionized water, and dried under a nitrogen atmosphere. Then, a transmission electron microscope (TEM) apparatus was used to determine whether there were residues remained on the surface of the film, and accordingly, detergency for the residues on surfaces was evaluated, and results thereof are shown in Table 1. The titanium/aluminum nitride film refers to a titanium nitride-containing film further including aluminum.
Referring to Table 1, it was confirmed that the cleaning compositions of Comparative Examples 1 to 4 did not substantially damage the surface of a target film under the cleaning performance conditions above, but had poor detergency, whereas the cleaning compositions of Comparative Examples 5 and 6 had excellent detergency, but damaged the surface of a target film under the cleaning performance conditions above. Meanwhile, it was confirmed that the cleaning compositions of Examples 1 to 3 did not substantially damage the surface of a target film under the cleaning performance conditions above, and at the same time, had excellent detergency.
A solvent was mixed with a cleaning accelerator (1 wt %) and a pH adjuster (1 wt %) shown in Table 2 to prepare cleaning compositions of Examples 11 to 14 and Comparative Example 11. Here, deionized water was used as the solvent, and an amount of the solvent corresponds to the remainder per 100 wt % of the cleaning composition.
Compounds 1, 2, 4, and A as the cleaning accelerators were each prepared in situ by mixing each of Compounds 1′, 2′, 4′, and A′ with NH4OH in equal molar amounts and Compound 2a as the cleaning accelerators was prepared in situ for use by mixing Compound 2′ with NH2CH2CH2OCH2CH2OH in equal molar amounts.
Subsequently, in the same manner as in Example 1, the etching speed and detergency for the residues on surfaces were evaluated with respect to the cleaning compositions of Examples 11 to 14 and Comparative Example 11, and the results thereof are shown in Table 2. The titanium/aluminum nitride film in Table 2 refers to a titanium nitride-containing film further including aluminum.
Referring to Table 2, it was confirmed that the cleaning composition of Comparative Example 11 did not substantially damage the surface of a target film to be cleaned under the cleaning performance conditions above, but had poor detergency, whereas the cleaning compositions of Examples 11 to 14 did not substantially damage the surface of a target film to be cleaned under the cleaning performance conditions above, and at the same time, had excellent detergency.
According to the one or more embodiments, a cleaning composition has excellent performance for removing residues on surfaces, and at the same time, does not damage a surface of a target film to be cleaned, and thus, by using the cleaning composition, the surface of a metal-containing film may be effectively cleaned and a high-performance semiconductor device may be manufactured.
It should be understood that embodiments described herein should be considered in a descriptive sense only and not for purposes of limitation. Descriptions of features or aspects within each embodiment should typically be considered as available for other similar features or aspects in other embodiments. While one or more embodiments have been described with reference to the figures, it will be understood by those of ordinary skill in the art that various changes in form and details may be made therein without departing from the spirit and scope as defined by the following claims.
| Number | Date | Country | Kind |
|---|---|---|---|
| 10-2022-0065552 | May 2022 | KR | national |
| 10-2022-0121142 | Sep 2022 | KR | national |
| 10-2023-0067189 | May 2023 | KR | national |
