Metal patterning method, metal adhesion improvement composition for semiconductor process, and manufacturing method thereof

Abstract

Provided are a metal patterning method, a metal adhesion improvement composition for the semiconductor process, and a method of manufacturing the same. The metal patterning method includes depositing a metal layer on a substrate; coating an adhesion improvement layer on the metal layer; applying an organic mask on the adhesion improvement layer; performing exposing and etching; and removing the organic mask and adhesion improvement layer, wherein the coating of an adhesion improvement layer on the metal layer includes coating a metal adhesion improvement composition for the semiconductor process on the metal layer followed by heating. By using the metal adhesion improvement composition for the semiconductor process of the present invention, resistance to wet etching can be enhanced during semiconductor processes, allowing metal patterning to be performed very effectively.

Description

CROSS-REFERENCE TO RELATED APPLICATION

[0001] This application claims priority to and the benefit of Korean Patent Application No. 10-2024-0095142 filed in the Korean Intellectual Property Office on Jul. 18, 2024, the entire contents of which are incorporated herein by reference.BACKGROUND OF THE INVENTIONField of the Invention

[0002] The present disclosure relates to a metal adhesion improvement composition for the semiconductor process, a method of manufacturing the same, and a metal patterning method the metal adhesion improvement composition for the semiconductor process during a semiconductor process using the composition for improving metal adhesion for a semiconductor process.

[0003] Description of the Related Art

[0004] In a process of forming a gate during a semiconductor process, a technology of wet-etching a gate metal in a desired region alone is applied to form multiple threshold voltages. In other words, a process of removing the gate metal in the region not covered with an organic mask through the wet etching but maintaining the other region covered with the organic mask is required.

[0005] As semiconductor devices have developed, because conventional organic masks have weak resistance to the wet etching as well as frequently cause an etching failure (unetching) problem during the dry etching process, development of a new organic mask is being explored. Accordingly, an organic mask containing an aromatic compound as an additive has been developed, but the additive brings about a new problem that a semiconductor process that can use the organic mask is very limited.

[0006] Accordingly, because there has been a need for a process of using the conventional organic mask with weak resistance to wet etching but having the same effect of increasing a wet etching patterning margin as a mask with excellent resistance to the wet etching, the present inventors have developed a process of satisfying the need after coating a metal on a substrate, by coating a separate adhesion improvement layer on the metal, before covering the metal with the organic mask.SUMMARY OF THE INVENTION

[0007] One aspect of the present disclosure provides a metal patterning method, a metal adhesion improvement composition for a semiconductor process, and a method for manufacturing the same, which enhance the resistance to wet etching of an organic mask through a metal adhesion improvement treatment process, and enable a metal patterning process among existing semiconductor processes to be more easily performed through the metal adhesion improvement treatment process even when an organic mask with low resistance to wet etching is used.

[0008] A metal patterning method according to one aspect includes depositing a metal layer on a substrate; coating an adhesion improvement layer on the metal layer; applying an organic mask on the adhesion improvement layer; etching the metal layer using the organic mask; and removing the organic mask and adhesion improvement layer from the etched metal layer, wherein the coating of the adhesion improvement layer on the metal layer includes coating a metal adhesion improvement composition on the metal layer and heating the metal adhesion improvement composition, and wherein the metal adhesion improvement composition includes a polymer comprising structural units represented by Chemical Formula 1 and Chemical Formula 2.

[0009] In Chemical Formula 1 and Chemical Formula 2,

[0010] R1 is a substituted or unsubstituted C1 to C20 alkyl group,

[0011] L1 is a single bond, a substituted or unsubstituted C1 to C20 alkylene group, *—C(═O)NH—*, or *—O—*, and

[0012] L2 is a single bond or a substituted or unsubstituted C1 to C20 alkylene group.

[0013] Chemical Formula 2 may be represented by at least one of Chemical Formula 2-1 or Chemical Formula 2-2.

[0014] The etching may include exposing the organic mask; dry etching the organic mask after the exposure such that regions of the organic mask are removed; and performing wet etching after the dry etching.

[0015] The polymer may include a structural unit represented by Chemical Formula 3.

[0016] In Chemical Formula 3, n:m=1:9 to 9:1.

[0017] In Chemical Formula 1 and Chemical Formula 2, R1 may be an unsubstituted C1 to C10 alkyl group, L1 may be *—C(═O)NH—*, and L2 may be a substituted or unsubstituted C1 to C20 alkylene group.

[0018] In Chemical Formula 3, n:m may be about 5:5 to about 9:1.

[0019] The polymer may have a weight average molecular weight of about 3000 g / mol to about 8000 g / mol.

[0020] The above polymer may include a structural unit represented by Chemical Formula 3-1.

[0021] The heating may be performed at about 100° C. to about 200° C.

[0022] The metal layer may include TiN.

[0023] The organic mask may be a catechol-based compound-free mask.

[0024] A metal adhesion improvement composition for the semiconductor process according to one aspect includes the polymer including structural units represented by Chemical Formula 1 and Chemical Formula 2.

[0025] The metal adhesion improvement composition for the semiconductor process may further include an organic solvent.

[0026] The polymer including structural units represented by Chemical Formula 1 and Chemical Formula 2 may be included in an amount of about 0.1 wt % to about 10 wt % based on a total amount of the metal adhesion improvement composition including the organic solvent.

[0027] The polymer including structural units represented by Chemical Formula 1 and Chemical Formula 2 may be included in an amount of about 1 wt % to about 5 wt % based on a total amount of the metal adhesion improvement composition including the organic solvent.

[0028] A method for manufacturing a metal adhesion improvement composition for the semiconductor process according to one aspect includes forming a copolymer by copolymerizing a monomer represented by Chemical Formula 4 and a monomer represented by Chemical Formula 5; and adding the copolymer to an organic solvent.

[0029] In Chemical Formula 4 and Chemical Formula 5,

[0030] R1 is a substituted or unsubstituted C1 to C20 alkyl group,

[0031] L1 is a single bond, a substituted or unsubstituted C1 to C20 alkylene group, *—C(═O)NH—*, or *—O—*, and

[0032] L2 is a single bond or a substituted or unsubstituted C1 to C20 alkylene group.

[0033] The copolymer may include the structural unit represented by Chemical Formula 3.

[0034] The copolymer may include a structural unit represented by Chemical Formula 3-1.

[0035] The metal patterning method according to one aspect includes coating an adhesion improvement layer on a metal layer using a metal adhesion improvement composition for a semiconductor process including the polymer of a specific structure before applying an organic mask thereto, so that even if an organic mask with insufficient resistance to wet etching is used, wet etching patterning of the metal layer can be more easily performed, and even when an organic mask with comparatively excellent resistance to wet etching is used, the resistance to wet etching of the organic mask can be further enhanced.BRIEF DESCRIPTION OF THE DRAWINGS

[0036] The above and other aspects and features of the present disclosure will become more apparent by describing in detail exemplary embodiments thereof with reference to the attached drawings, in which:

[0037] FIG. 1 is a drawing sequentially showing a metal patterning method according to one aspect including dry and wet etching processes during a semiconductor process.

[0038] FIG. 2 is a drawing sequentially showing a metal patterning method including dry and wet etching processes among conventional semiconductor processes.

[0039] FIG. 3 is a photograph showing the spacing between gate metal layers after patterning the metal layers using the metal patterning method according to Example 1.

[0040] FIG. 4 is a photograph showing the spacing between gate metal layers before patterning the metal layers using the metal patterning method according to Example 1.

[0041] FIG. 5 is an XPS (X-ray Photoelectron Spectroscopy) graph when the coating conditions (heating temperature during coating, etc.) of the adhesion improvement layer are changed during patterning of the metal layer by a metal patterning method according to one aspect.

[0042] FIG. 6 is a photograph for confirming whether metal remains in a portion that is covered with an organic mask and a portion that is not covered after patterning a metal layer using the metal patterning method according to Example 1.

[0043] FIG. 7 is a photograph for confirming whether metal remains in a portion that is covered with an organic mask and a portion that is not covered after patterning a metal layer using the metal patterning method according to Comparative Example 1.DETAILED DESCRIPTION OF THE EMBODIMENTS

[0044] The present invention will be described more fully hereinafter with reference to the accompanying drawings, in which example embodiments of the invention are shown. As those skilled in the art would realize, the described embodiments may be modified in various different ways, all without departing from the spirit or scope of the present invention.

[0045] The drawings and description are to be regarded as illustrative in nature and not restrictive. Like reference numerals designate like elements throughout the specification.

[0046] The size and thickness of each constituent element as shown in the drawings are provided for better understanding and ease of description, and the disclosure is not necessarily limited to as shown. In the drawings, the thickness of layers, films, panels, regions, etc., may be exaggerated for clarity. In addition, in the drawings, for better understanding and ease of description, the thickness of some layers and areas may be exaggerated. Additionally, when the terms “about” or “substantially” are used in this specification in connection with a numerical value and / or geometric terms, it is intended that the associated numerical value includes a manufacturing tolerance (e.g., ±10%) around the stated numerical value. Further, regardless of whether numerical values and / or geometric terms are modified as “about” or “substantially,” it will be understood that these values should be construed as including a manufacturing or operational tolerance (e.g., ±10%) around the stated numerical values and / or geometric. When referring to “C to D”, this means C inclusive to D inclusive unless otherwise specified.

[0047] It will be understood that when an element such as a layer, film, region, or substrate is referred to as being “on” another element, it can be directly on the other element or intervening elements may also be present. In contrast, when an element is referred to as being “directly on” another element, there are no intervening elements present. Additionally, the word “on” or “above” means being disposed on or below the object portion, and does not necessarily mean being disposed on the upper side of the object portion based on a gravitational direction. More specifically, it will be understood that such spatially relative terms, such as “above”, “top”, etc., are intended to encompass different orientations of the device in use or operation in addition to the orientation depicted in the figures, and that the device may be otherwise oriented (rotated 90 degrees or at other orientations) and the spatially relative terms used herein interpreted accordingly.

[0048] In addition, unless explicitly described to the contrary, the word “comprise”, and variations such as “comprises” or “comprising”, will be understood to imply the inclusion of stated elements but not the exclusion of any other elements.

[0049] In addition, throughout the specification, when referring to “plane,” it means when the target part is viewed from above, and when referring to “cross section,” it means when viewing the cross section of the target portion vertically cut from the side.

[0050] The present disclosure relates to a metal patterning method of further enhancing resistance to wet etching of an organic mask for wet etching, which is used in the metal patterning process during the semiconductor process, and / or easing a metal patterning process with an organic mask with insufficient resistance to wet etching, which is not used in a conventional semiconductor process, a metal adhesion improvement composition for a semiconductor process used in the metal patterning method, and a method for manufacturing the same and in particular, after depositing a metal layer on a substrate but before applying an organic mask, applying the metal adhesion improvement composition for a semiconductor process on the metal layer and then, heating it to form an adhesion improvement layer thereon. Accordingly, the metal patterning process including the wet etching process may offer a wide range of available organic mask options and also, enhance resistance to wet etching of an organic mask, resulting in having an effect of increasing a patterning margin. In other words, through the adhesion improvement layer coating according to one aspect, in all layers requiring wet etching patterning, the wet etching patterning may not only be easily performed, but also, even if an organic mask with insufficient wet etching resistance is used, because wet etching resistance of the organic mask is enhanced, there may be an effect of improving a wet etching patterning process margin.

[0051] Conventionally, in order to prevent or reduce peeling between an organic mask and a metal layer, after enhancing resistance to wet etching of an organic mask by separately adding an additive for improving adhesion, for example, an aromatic compound (monomer) to the organic mask, the organic mask with enhanced resistance to wet etching is used to proceed with metal patterning, wherein there is a problem of limiting available types of organic mask according to the use of only an organic mask with enhanced resistance to wet etching. In addition, the addition of the additive for improving adhesion may bring about another problem of slowing down an etching rate during the dry etching.

[0052] Specifically, conventionally, when a scheme of coating an organic mask directly on a metal to be patterned and performing metal patterning is used, the conventional organic mask is not suited to perform the metal patterning due to insufficient resistance to wet etching (refer to FIG. 2), which may result in unwanted etching, such as under-etching. However, an adhesion improvement layer, if coated before coating an organic mask, may enhance resistance to wet etching of the organic mask, resulting in making it possible to use the conventional organic mask.

[0053] That is, as shown in FIG. 1, by applying an organic mask after performing an adhesion improvement layer coating, it is possible to manufacture a metal layer with excellent patternability even when using a conventional organic mask.

[0054] In other words, a metal patterning method according to one aspect includes depositing a metal layer on a substrate; coating an adhesion improvement layer on the metal layer; applying an organic mask on the adhesion improvement layer; performing exposing and etching; and removing the organic mask and adhesion improvement layer, wherein the coating of the adhesion improvement layer on the metal layer includes coating a metal adhesion improvement composition for a semiconductor process, which will be described later, on the metal layer and heating.

[0055] Referring to FIG. 1, in at least some embodiments, after coating the adhesion improvement layer onto the metal layer, a strip process may be further included before applying an organic mask.

[0056] Referring to FIG. 1, performing the exposing and etching may include exposing (or developing) a region of the organic mask such that a portion of the organic mask is reacted (e.g., cross-polymerized); dry etching after the exposure such that a region of the organic mask is removed and a region (corresponding to a desired pattern) remains; and performing wet etching after the dry etching such that the metal layer exposed by the dry etching is removed. In at least some embodiments, the exposing may include exposing regions of the organic mask to light, such that a photo-sensitive reaction occurs. In general, in the case of dry etching, electrical energy is applied to cause a reaction of an etching gas, converting the etching gas into a plasma state, and then the ions generated at this time are used to cause an etching reaction, e.g., with undeveloped regions of the organic mask. Since the ions travel in a straight line, anisotropic etching is performed in which etching is performed only in the vertical direction, so there is little to no concern about etching defects. However, in the case of wet etching, since the etching reaction is performed using an etchant, isotropic etching is performed in which etching is performed in both the horizontal and vertical directions, so there is a very high concern about etching defects occurring (see the wet etch portion of FIG. 2). However, since the metal patterning method according to one aspect includes coating an adhesion improvement layer on a metal layer before the exposing and etching steps and then applies an organic mask and then performing the exposing and etching process, the occurrence of etching defects can be significantly suppressed even in a wet etching process in which isotropic etching is performed.

[0057] After coating the metal adhesion improvement composition for the semiconductor process on the metal layer, heating is performed for coating. For example, the heating may be performed at about 100° C. to about 200° C., for example, about 110° C. to about 180° C. In at least some embodiments, if the heating is not performed, there is a risk that the coating will not be performed well and the metal patterning will proceed without forming an adhesion improvement layer. However, when the heating temperature exceeds about 200° C., there is no significant difference in the coating properties compared to when heating at a lower temperature, for example, a temperature of about 100° C. to about 200° C. More specifically, since there is a concern that the coating property may deteriorate when the heating temperature is lower than about 100° C., the heating temperature may be controlled to about 100° C. to about 200° C., for example, about 110° C. to about 180° C.

[0058] In at least some examples, the metal layer may include at least one of TiN, AlO, LaO, and / or a combination thereof.

[0059] In at least some examples, the organic mask may be an organic mask with enhanced resistance to wet etching, including, for example, a catechol-based compound.

[0060] Alternatively, in at least some examples, the organic mask may be a catechol-based compound-free organic mask that does not include a catechol-based compound and has poor resistance to wet etching.

[0061] The catechol-based compound may include a catechol compound and / or a derivative thereof.

[0062] Meanwhile, the metal adhesion improvement composition for the semiconductor process includes a polymer including structural units represented by Chemical Formula 1 and Chemical Formula 2.

[0063] In Chemical Formula 1 and Chemical Formula 2,

[0064] R1 is a substituted or unsubstituted C1 to C20 alkyl group,

[0065] L1 is a single bond, a substituted or unsubstituted C1 to C20 alkylene group, *—C(═O)NH—*, or *—O—*, and

[0066] L2 is a single bond or a substituted or unsubstituted C1 to C20 alkylene group. In at least some examples, when one of L1 or L2 is a single bond, the other is not a single bond.

[0067] Since the metal adhesion improvement composition for the semiconductor process includes the polymer including structural units represented by Chemical Formula 1 and Chemical Formula 2, the adhesion improvement coating layer has excellent adhesion to the metal layer, and thus can exhibit the above-described effect.

[0068] For example, the structural unit represented by Chemical Formula 1 enables the lowering of the glass transition temperature of the metal adhesion improvement composition for the semiconductor process, and the structural unit represented by Chemical Formula 2 enables the improving of the resistance to wet etching of the metal adhesion improvement composition for the semiconductor process, ultimately improving the resistance to wet etching of the organic mask. If the glass transition temperature of the metal adhesion improvement composition for the semiconductor process is high, the gap fill ability for filling fine gaps is deteriorated, making it difficult, if not impossible, to cover fine gaps with an adhesion improvement coating layer. In addition, if the resistance to wet etching of the metal adhesion improvement composition for the semiconductor process is inferior, there is a concern that the metal layer in the area covered with the organic mask may be partially and / or completely lost when the wet etching process is performed, thereby resulting in etching occurring in unwanted areas. That is, the polymer included in the metal adhesion improvement composition for the semiconductor process must include both the structural unit represented by Chemical Formula 1 and the structural unit represented by Chemical Formula 2. If it does not include either of these, the adhesion improvement coating layer is not properly coated on the metal layer and / or the effect of improving resistance to wet etching is not achieved.

[0069] In at least some examples, the structural unit represented by Chemical Formula 1 and the structural unit represented by Chemical Formula 2 may be included in a molar ratio of about 1:9 to about 9:1.

[0070] In at least some examples, Chemical Formula 2 may be represented by Chemical Formula 2-1 and / or Chemical Formula 2-2. In these cases, the coating properties of the adhesion improvement coating layer for the metal layer can be further enhanced, and the effect of improving resistance to wet etching can be considered to be very excellent.

[0071] In Chemical Formula 2-1 and Chemical Formula 2-2,

[0072] L1 is a single bond, a substituted or unsubstituted C1 to C20 alkylene group, *—C(═O)NH—*, or *—O—*, and

[0073] L2 is a single bond or a substituted or unsubstituted C1 to C20 alkylene group.

[0074] For example, the polymer may include a structural unit represented by Chemical Formula 3.

[0075] In Chemical Formula 3,

[0076] R1 is a substituted or unsubstituted C1 to C20 alkyl group,

[0077] L1 is a single bond, a substituted or unsubstituted C1 to C20 alkylene group, *—C(═O)NH—*, or *—O—*,

[0078] L2 is a single bond or a substituted or unsubstituted C1 to C20 alkylene group, and n:m=1:9 to 9:1.

[0079] For example, in Chemical Formula 1 to Chemical Formula 3, R1 may be an unsubstituted C1 to C10 alkyl group, L1 may be *—C(═O)NH—*, and L2 may be a substituted or unsubstituted C1 to C20 alkylene group, In these cases.

[0080] In at least some examples, in Chemical Formula 3, n: m may be 5:5 to 9:1. In these cases, since the structural unit represented by Chemical Formula 2 is included in a relatively larger amount than the structural unit represented by Chemical Formula 1, the above-described effect can be further increased.

[0081] For example, Chemical Formula 3 may be represented by Chemical Formula 3-1.

[0082] For example, the polymer may have a weight average molecular weight of about 3000 g / mol to about 8000 g / mol. When the weight average molecular weight of the polymer is within the above range, the effect of improving adhesion to the metal layer may be further doubled.

[0083] For example, the metal adhesion improvement composition for the semiconductor process may further include an organic solvent. At this time, the organic solvent is not particularly limited in type. For example, the organic solvent may be selected based on compatibility and reactivity with the other elements in the process, and may include, e.g., alcohols such as methanol, ethanol, and / or the like; ethers such as dichloroethyl ether, n-butyl ether, diisoamyl ether, methylphenyl ether, tetrahydrofuran, and / or the like; glycol ethers such as ethylene glycol monomethylether, ethylene glycol monoethylether, and / or the like; cellosolve acetates such as methyl cellosolve acetate, ethyl cellosolve acetate, diethyl cellosolve acetate, and / or the like; carbitols such as methylethyl carbitol, diethyl carbitol, diethylene glycol monomethylether, diethylene glycol monoethylether, diethylene glycol dimethylether, diethylene glycol methylethylether, diethylene glycol diethylether, and / or the like; propylene glycol alkylether acetates such as propylene glycol methylether acetate, propylene glycol propylether acetate, and / or the like; aromatic hydrocarbons such as toluene, xylene and / or the like; ketones such as methylethylketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, methyl-n-propylketone, methyl-n-butylketone, methyl-n-amylketone, 2-heptanone, and / or the like; saturated aliphatic monocarboxylic acid alkyl esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, and / or the like; lactate esters such as methyl lactate, ethyl lactate, and / or the like; oxy acetic acid alkyl esters such as oxy methyl acetate, oxy ethyl acetate, butyl oxyacetate, and / or the like; alkoxy acetic acid alkyl esters such as methoxy methyl acetate, methoxy ethyl acetate, methoxy butyl acetate, ethoxy methyl acetate, ethoxy ethyl acetate, and / or the like; 3-oxy propionic acid alkyl esters such as 3-oxy methyl propionate, 3-oxy ethyl propionate, and / or the like; 3-alkoxy propionic acid alkyl esters such as 3-methoxy methyl propionate, 3-methoxy ethyl propionate, 3-ethoxy ethyl propionate, 3-ethoxy methyl propionate, and / or the like; 2-oxy propionic acid alkyl esters such as 2-oxy methyl propionate, 2-oxy ethyl propionate, 2-oxy propyl propionate, and / or the like; 2-alkoxy propionic acid alkyl esters such as 2-methoxy methyl propionate, 2-methoxy ethyl propionate, 2-ethoxy ethyl propionate, 2-ethoxy methyl propionate, and / or the like; 2-oxy-2-methyl propionic acid esters such 2-oxy-2-methyl methyl propionate, 2-oxy-2-methyl ethyl propionate, and / or the like, monooxy monocarboxylic acid alkyl esters of 2-alkoxy-2-methyl alkyl propionates such as 2-methoxy-2-methyl methyl propionate, 2-ethoxy-2-methyl ethyl propionate, and / or the like; esters such as 2-hydroxy ethyl propionate, 2-hydroxy-2-methyl ethyl propionate, hydroxy ethyl acetate, 2-hydroxy-3-methyl methyl butanoate, and / or the like; ketonate esters such as ethyl pyruvate, and / or the like. Additionally, high boiling point solvent such as N-methylformamide, N,N-dimethylformamide, N-methylformanilide, N-methylacetamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, benzylethylether, dihexylether, acetylacetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzylalcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, phenyl cellosolve acetate, and / or the like may be also used.

[0084] Among these, considering compatibility and reactivity, examples thereof include ketones such as cyclohexanone; glycol ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; ethylene glycol alkyl ether acetates such as ethyl cellosolve acetate; esters such as ethyl 2-hydroxypropionate; carbitols such as diethylene glycol monomethyl ether; and propylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate and propylene glycol propyl ether acetate.

[0085] For example, the polymer including structural units represented by Chemical Formula 1 and Chemical Formula 2 may be included in an amount of about 0.1 percent by weight (wt %) to about 10 wt %, for example about 1 wt % to about 5 wt % based on a total amount of the metal adhesion improvement composition including the organic solvent. When the polymer is included within the above range, the adhesion improvement composition for a semiconductor process can have an appropriate viscosity and thus have excellent processability during coating.

[0086] According to one aspect, a method for manufacturing the adhesion improvement composition for a semiconductor process is provided. Specifically, the method includes forming a copolymer by copolymerizing a monomer represented by Chemical Formula 4 and a monomer represented by Chemical Formula 5; and adding the copolymer to an organic solvent.

[0087] In Chemical Formula 4 and Chemical Formula 5,

[0088] R1 is a substituted or unsubstituted C1 to C20 alkyl group,

[0089] L1 is a single bond, a substituted or unsubstituted C1 to C20 alkylene group, *—C(═O)NH—*, or *—O—*, and

[0090] L2 is a single bond or a substituted or unsubstituted C1 to C20 alkylene group.

[0091] The monomer represented by Chemical Formula 4 may be copolymerized to form a structural unit represented by Chemical Formula 1, and the monomer represented by Chemical Formula 5 may be copolymerized to form a structural unit represented by Chemical Formula 2. In at least some examples, the copolymerization may include a chain growth polymerization reaction. Accordingly, the copolymer may include a structural unit represented by Chemical Formula 3, more specifically, a structural unit represented by Chemical Formula 3-1.

[0092] Although the exemplary embodiments have been described above, they are not limited to the exemplary embodiments described above, and various additions, omissions, substitutions, and changes may be made. Additionally, it is possible to form other embodiments by combining elements in different embodiments.

[0093] Hereinafter, various experiments using a metal adhesion improvement composition for the semiconductor process according to an embodiment are described. The experiments described below do not limit the present disclosure.EXAMPLESSynthesis of PolymersSynthesis Example 1:

[0094] A polymer (a weight average molecular weight: 6000 g / mol) containing a structural unit represented by Chemical Formula 3-1 was synthesized by free radical polymerization (using AIBN as an initiator) of a butyl acrylate monomer and a dopamine monomer at 60° C.Synthesis Example 2:

[0095] A polymer (a weight average molecular weight: 4000 g / mol) containing a structural unit represented by Chemical Formula 3-2 was synthesized in the same manner as in Synthesis Example 1 except that contents of the butyl acrylate monomer and the dopamine monomer were changed.Synthesis Example 3:

[0096] A polymer (a weight average molecular weight: 7200 g / mol) containing a structural unit represented by Chemical Formula 3-3 was synthesized in the same manner as in Synthesis Example 1 except that contents of the butyl acrylate monomer and the dopamine monomer were changed.Synthesis Example 4:

[0097] A polymer (a weight average molecular weight: 8000 g / mol) containing a structural unit represented by Chemical Formula 3-4 was synthesized in the same manner as in Synthesis Example 1 except that contents of the butyl acrylate monomer and the dopamine monomer were changed.Synthesis Example 5:

[0098] A polymer (a weight average molecular weight: 3000 g / mol) containing a structural unit represented by Chemical Formula 3-5 was synthesized in the same manner as in Synthesis Example 1 except that contents of the butyl acrylate monomer and the dopamine monomer were changed.Synthesis Example 6:

[0099] A polymer (a weight average molecular weight: 8400 g / mol) containing a structural unit represented by Chemical Formula 3-6 was synthesized in the same manner as in Synthesis Example 1 except that contents of the butyl acrylate monomer and the dopamine monomer were changed.Synthesis Example 7:

[0100] A polymer (a weight average molecular weight: 2800 g / mol) containing a structural unit represented by Chemical Formula 3-7 was synthesized in the same manner as in Synthesis Example 1 except that contents of the butyl acrylate monomer and the dopamine monomer were changed.Synthesis Example 8:

[0101] A polymer (a weight average molecular weight: 6600 g / mol) containing a structural unit represented by Chemical Formula 3-8 was synthesized in the same manner as in Synthesis Example 1 except that 2-ethylhexylacrylate was used instead of the butyl acrylate monomer.Synthesis Example 9:

[0102] A polymer (a weight average molecular weight: 8700 g / mol) containing a structural unit represented by Chemical Formula 3-9 was synthesized in the same manner as in Synthesis Example 1 except that a stearyl acrylate monomer was used instead of the butyl acrylate monomer.Synthesis Example 10:

[0103] A polymer (a weight average molecular weight: 6000 g / mol) containing a structural unit represented by Chemical Formula 3-10 was synthesized in the same manner as in Synthesis Example 1 except that types of the dopamine monomer was changed.Comparative Synthesis Example 1:

[0104] A polymer was synthesized in the same manner as in Synthesis Example 1 except that the dopamine monomer was not used.Comparative Synthesis Example 2:

[0105] A polymer was synthesized in the same manner as in Synthesis Example 1 except that the butyl acrylate monomer was not used.Preparation of Metal Adhesion Improvement Composition for Semiconductor ProcessPreparation Example 1-1:

[0106] A metal adhesion improvement composition for a semiconductor process was prepared by dissolving the polymer of Synthesis Example 1 in a PGME solvent to be 4 wt % based on the total composition.Preparation Example 1-2:

[0107] A metal adhesion improvement composition for a semiconductor process was prepared by dissolving the polymer of Synthesis Example 1 in a PGME solvent to be 0.1 wt % based on the total composition.Preparation Example 1-3:

[0108] A metal adhesion improvement composition for a semiconductor process was prepared by dissolving the polymer of Synthesis Example 1 in a PGME solvent to be 0.05 wt % based on the total composition.Preparation Example 1-4:

[0109] A metal adhesion improvement composition for a semiconductor process was prepared by dissolving the polymer of Synthesis Example 1 in a PGME solvent to be 1 wt % based on the total composition.Preparation Example 1-5:

[0110] A metal adhesion improvement composition for a semiconductor process was prepared by dissolving the polymer of Synthesis Example 1 in a PGME solvent to be 7 wt % based on the total composition.Preparation Example 1-6:

[0111] A metal adhesion improvement composition for a semiconductor process was prepared by dissolving the polymer of Synthesis Example 1 in a PGME solvent to be 10 wt % based on the total composition.Preparation Example 1-7:

[0112] A metal adhesion improvement composition for a semiconductor process was prepared by dissolving the polymer of Synthesis Example 1 in a PGME solvent to be 11 wt % based on the total composition.Preparation Example 2:

[0113] A metal adhesion improvement composition for a semiconductor process was prepared in the same manner as in Preparation Example 1 except that the polymer of Synthesis Example 2 was used instead of the polymer of Synthesis Example 1.Preparation Example 3:

[0114] A metal adhesion improvement composition for a semiconductor process was prepared in the same manner as in Preparation Example 1 except that the polymer of Synthesis Example 3 was used instead of the polymer of Synthesis Example 1.Preparation Example 4:

[0115] A metal adhesion improvement composition for a semiconductor process was prepared in the same manner as in Preparation Example 1 except that the polymer of Synthesis Example 4 was used instead of the polymer of Synthesis Example 1.Preparation Example 5:

[0116] A metal adhesion improvement composition for a semiconductor process was prepared in the same manner as in Preparation Example 1 except that the polymer of Synthesis Example 5 was used instead of the polymer of Synthesis Example 1.Preparation Example 6:

[0117] A metal adhesion improvement composition for a semiconductor process was prepared in the same manner as in Preparation Example 1 except that the polymer of Synthesis Example 6 was used instead of the polymer of Synthesis Example 1.Preparation Example 7:

[0118] A metal adhesion improvement composition for a semiconductor process was prepared in the same manner as in Preparation Example 1 except that the polymer of Synthesis Example 7 was used instead of the polymer of Synthesis Example 1.Preparation Example 8:

[0119] A metal adhesion improvement composition for a semiconductor process was prepared in the same manner as in Preparation Example 1 except that the polymer of Synthesis Example 8 was used instead of the polymer of Synthesis Example 1.Preparation Example 9:

[0120] A metal adhesion improvement composition for a semiconductor process was prepared in the same manner as in Preparation Example 1 except that the polymer of Synthesis Example 9 was used instead of the polymer of Synthesis Example 1.Preparation Example 10:

[0121] A metal adhesion improvement composition for a semiconductor process was prepared in the same manner as in Preparation Example 1 except that the polymer of Synthesis Example 10 was used instead of the polymer of Synthesis Example 1.Comparative Preparation Example 1:

[0122] A metal adhesion improvement composition for a semiconductor process was prepared in the same manner as in Preparation Example 1 except that the polymer of Comparative Synthesis Example 1 was used instead of the polymer of Synthesis Example 1.Comparative Preparation Example 2:

[0123] A metal adhesion improvement composition for a semiconductor process was prepared in the same manner as in Preparation Example 1 except that the polymer of Comparative Synthesis Example 2 was used instead of the polymer of Synthesis Example 1.Metal PatterningExample 1

[0124] After depositing TiN on a substrate, the composition of Preparation Example 1-1 was coated on the TiN and then, heated at 110° C. to coat an adhesion improvement layer thereon. Subsequently, after applying an organic mask on the coated adhesion improvement layer exposure and etching proceeded, and lastly, the organic mask and the adhesion improvement layer were peeled off to perform TiN patterning.Example 2

[0125] TiN patterning proceeded in the same manner as in Example 1 except that the heating temperature for coating the adhesion improvement layer was changed from 110° C. to 180° C.Example 3: (Reference)

[0126] TiN patterning proceeded in the same manner as in Example 1 except that the heating temperature for coating the adhesion improvement layer was changed from 110° C. to 90° C.Example 4: (For Reference Only)

[0127] TiN patterning proceeded in the same manner as in Example 1 except that the composition of Preparation Example 1-2 was used instead of the composition of Preparation Example 1-1.Example 5: (Reference)

[0128] TiN patterning proceeded in the same manner as in Example 1 except that the composition of Preparation Example 1-3 was used instead of the composition of Preparation Example 1-1.Example 6

[0129] TiN patterning proceeded in the same manner as in Example 1 except that the composition of Preparation Example 1-4 was used instead of the composition of Preparation Example 1-1.Example 7

[0130] TiN patterning proceeded in the same manner as in Example 1 except that the composition of Preparation Example 1-5 was used instead of the composition of Preparation Example 1-1.Example 8: (For Reference)

[0131] TiN patterning proceeded in the same manner as in Example 1 except that the composition of Preparation Example 1-6 was used instead of the composition of Preparation Example 1-1.Example 9: (For Reference)

[0132] TiN patterning proceeded in the same manner as in Example 1 except that the composition of Preparation Example 1-7 was used instead of the composition of Preparation Example 1-1.Example 10

[0133] TiN patterning proceeded in the same manner as in Example 1 except that the composition of Preparation Example 2 was used instead of the composition of Preparation Example 1-1.Example 11

[0134] TiN patterning proceeded in the same manner as in Example 1 except that the composition of Preparation Example 3 was used instead of the composition of Preparation Example 1-1.Example 12

[0135] TiN patterning proceeded in the same manner as in Example 1 except that the composition of Preparation Example 4 was used instead of the composition of Preparation Example 1-1.Example 13

[0136] TiN patterning proceeded in the same manner as in Example 1 except that the composition of Preparation Example 5 was used instead of the composition of Preparation Example 1-1.Example 14: (For Reference)

[0137] TiN patterning proceeded in the same manner as in Example 1 except that the composition of Preparation Example 6 was used instead of the composition of Preparation Example 1-1.Example 15: (For Reference)

[0138] TiN patterning proceeded in the same manner as in Example 1 except that the composition of Preparation Example 7 was used instead of the composition of Preparation Example 1-1.Example 16

[0139] TiN patterning proceeded in the same manner as in Example 1 except that the composition of Preparation Example 8 was used instead of the composition of Preparation Example 1-1.Example 17: (For Reference)

[0140] TiN patterning proceeded in the same manner as in Example 1 except that the composition of Preparation Example 9 was used instead of the composition of Preparation Example 1-1.Example 18

[0141] TiN patterning proceeded in the same manner as in Example 1 except that the composition of Preparation Example 10 was used instead of the composition of Preparation Example 1-1.Comparative Example 1

[0142] TiN patterning proceeded in the same manner as in Example 1 except that the adhesion improvement layer was not formed by coating the composition of Preparation Example 1-1.Comparative Example 2

[0143] TiN patterning proceeded in the same manner as in Example 1 except that the composition of Comparative Preparation Example 1 was used instead of the composition of Preparation Example 1-1.Comparative Example 3

[0144] TiN patterning proceeded in the same manner as in Example 1 except that the composition of Comparative Preparation Example 2 was used instead of the composition of Preparation Example 1-1.Comparative Example 4

[0145] TiN patterning proceeded in the same manner as in Example 1 except that the heating process for coating the adhesion improvement layer was not performed.(Evaluation 1)

[0146] In the metal layers (TiN) patterned according to the methods according to Examples 1 to 18 and Comparative Examples 1 to 4, after depositing each of the metal layers on a substrate, a thickness (gap) between the metal layers was checked, and subsequently, after coating an adhesion improvement layer thereon and performing a peeling process by using an ArF thinner (up to the strip process of FIG. 1), the thickness (gap) between the metal layers was checked again, and the results are shown in Tables 1 to 3 and FIGS. 3 and 4. Referring to Table 1 and FIGS. 3 and 4. in the metal layer patterned in the method of Example 1. the adhesion improvement layer was respectively coated to have a thickness of 2 nm on the metal layer.TABLE 1(unit: nm)Examples123456789Gap before coating adhesion161616161616161616improvement layerGap after coating adhesion121214131412121314improvement layerTABLE 2(unit: nm)Examples101112131415161718Gap before coating adhesion161616161616161616improvement layerGap after coating adhesion121212121414121412improvement layerTABLE 3(unit: nm)ComparativeComparativeComparativeComparativeExample 1Example 2Example 3Example 4Gap before coating16161616adhesion improvementlayerGap after coating—151516adhesion improvementlayerReferring to Table 3, in Comparative Example 1, which had no adhesion improvement layer coating, there was no gap data after the adhesion improvement layer coating, and in Comparative Examples 2 to 4, the adhesion improvement layer was almost not coated.(Evaluation 2)After coating the adhesion improvement layer in Example 1, Example 2, Comparative Examples 1 and 4 of Evaluation 1 and performing the peeling process by using an ArF thinner (up to the strip process of FIG. 1), the metal layer patterns were subjected to XPS analysis, and the results are shown in FIG. 5.

[0149] Referring to FIG. 5, through XPS, it was confirmed that after the adhesion improvement layer coating, a Ti peak decreased, but a C═O peak of the adhesion improvement layer increased and in particular, became saturated from a temperature of 110° C. or more. In other words, in order to coat an adhesion improvement composition for a semiconductor process on a metal layer on a substrate, a heating process is necessary to perform, and the heating temperature of 110° C. or higher was confirmed to be sufficient for the heating process.(Evaluation 3)

[0150] The metal layers (TiN) respectively patterned in the methods according to Examples 1 to 18 and Comparative Examples 1 to 4 were taken a scanning electron microscope (SEM) image of to check whether TiN was present or not in a region (wet block) covered with an organic mask, and the results are shown in Tables 4 to 6 and FIGS. 6 and 7. In Tables 4 to 6, if TiN was confirmed on a scanning electron microscope image, ○ was given, but if not confirmed, X was given. Referring to Tables 4 and 6 and FIGS. 6 and 7, the metal layer patterned in the method of Example 1 exhibited that TIN was present in the region covered with the organic mask, but the metal layer patterned in the method of Comparative Example 1 exhibited that TiN was all lost equally even in the region covered with the organic mask like in the region (wet open) not covered with the organic mask.TABLE 4Examples123456789Presence or absence of TiN◯◯X◯X◯◯◯Xin the region covered withorganic maskTABLE 5Examples101112131415161718Presence or absence of TiN◯◯◯◯XX◯X◯in the region covered withorganic maskTABLE 6ComparativeComparativeComparativeComparativeExample 1Example 2Example 3Example 4Presence or absence ofXXXXTiN in the regioncovered with organicmaskWhile this invention has been described in connection with what is presently considered to be practical exemplary embodiments, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims.

Examples

synthesis example 1

[0094]A polymer (a weight average molecular weight: 6000 g / mol) containing a structural unit represented by Chemical Formula 3-1 was synthesized by free radical polymerization (using AIBN as an initiator) of a butyl acrylate monomer and a dopamine monomer at 60° C.

synthesis example 2

[0095]A polymer (a weight average molecular weight: 4000 g / mol) containing a structural unit represented by Chemical Formula 3-2 was synthesized in the same manner as in Synthesis Example 1 except that contents of the butyl acrylate monomer and the dopamine monomer were changed.

synthesis example 3

[0096]A polymer (a weight average molecular weight: 7200 g / mol) containing a structural unit represented by Chemical Formula 3-3 was synthesized in the same manner as in Synthesis Example 1 except that contents of the butyl acrylate monomer and the dopamine monomer were changed.

CROSS-REFERENCE TO RELATED APPLICATION

[0001] This application claims priority to and the benefit of Korean Patent Application No. 10-2024-0095142 filed in the Korean Intellectual Property Office on Jul. 18, 2024, the entire contents of which are incorporated herein by reference.BACKGROUND OF THE INVENTIONField of the Invention

[0002] The present disclosure relates to a metal adhesion improvement composition for the semiconductor process, a method of manufacturing the same, and a metal patterning method the metal adhesion improvement composition for the semiconductor process during a semiconductor process using the composition for improving metal adhesion for a semiconductor process.

[0003] Description of the Related Art

[0004] In a process of forming a gate during a semiconductor process, a technology of wet-etching a gate metal in a desired region alone is applied to form multiple threshold voltages. In other words, a process of removing the gate metal in the region not covered with an organic mask through the wet etching but maintaining the other region covered with the organic mask is required.

[0005] As semiconductor devices have developed, because conventional organic masks have weak resistance to the wet etching as well as frequently cause an etching failure (unetching) problem during the dry etching process, development of a new organic mask is being explored. Accordingly, an organic mask containing an aromatic compound as an additive has been developed, but the additive brings about a new problem that a semiconductor process that can use the organic mask is very limited.

[0006] Accordingly, because there has been a need for a process of using the conventional organic mask with weak resistance to wet etching but having the same effect of increasing a wet etching patterning margin as a mask with excellent resistance to the wet etching, the present inventors have developed a process of satisfying the need after coating a metal on a substrate, by coating a separate adhesion improvement layer on the metal, before covering the metal with the organic mask.SUMMARY OF THE INVENTION

[0007] One aspect of the present disclosure provides a metal patterning method, a metal adhesion improvement composition for a semiconductor process, and a method for manufacturing the same, which enhance the resistance to wet etching of an organic mask through a metal adhesion improvement treatment process, and enable a metal patterning process among existing semiconductor processes to be more easily performed through the metal adhesion improvement treatment process even when an organic mask with low resistance to wet etching is used.

[0008] A metal patterning method according to one aspect includes depositing a metal layer on a substrate; coating an adhesion improvement layer on the metal layer; applying an organic mask on the adhesion improvement layer; etching the metal layer using the organic mask; and removing the organic mask and adhesion improvement layer from the etched metal layer, wherein the coating of the adhesion improvement layer on the metal layer includes coating a metal adhesion improvement composition on the metal layer and heating the metal adhesion improvement composition, and wherein the metal adhesion improvement composition includes a polymer comprising structural units represented by Chemical Formula 1 and Chemical Formula 2.

[0009] In Chemical Formula 1 and Chemical Formula 2,

[0010] R1 is a substituted or unsubstituted C1 to C20 alkyl group,

[0011] L1 is a single bond, a substituted or unsubstituted C1 to C20 alkylene group, *—C(═O)NH—*, or *—O—*, and

[0012] L2 is a single bond or a substituted or unsubstituted C1 to C20 alkylene group.

[0013] Chemical Formula 2 may be represented by at least one of Chemical Formula 2-1 or Chemical Formula 2-2.

[0014] The etching may include exposing the organic mask; dry etching the organic mask after the exposure such that regions of the organic mask are removed; and performing wet etching after the dry etching.

[0015] The polymer may include a structural unit represented by Chemical Formula 3.

[0016] In Chemical Formula 3, n:m=1:9 to 9:1.

[0017] In Chemical Formula 1 and Chemical Formula 2, R1 may be an unsubstituted C1 to C10 alkyl group, L1 may be *—C(═O)NH—*, and L2 may be a substituted or unsubstituted C1 to C20 alkylene group.

[0018] In Chemical Formula 3, n:m may be about 5:5 to about 9:1.

[0019] The polymer may have a weight average molecular weight of about 3000 g / mol to about 8000 g / mol.

[0020] The above polymer may include a structural unit represented by Chemical Formula 3-1.

[0021] The heating may be performed at about 100° C. to about 200° C.

[0022] The metal layer may include TiN.

[0023] The organic mask may be a catechol-based compound-free mask.

[0024] A metal adhesion improvement composition for the semiconductor process according to one aspect includes the polymer including structural units represented by Chemical Formula 1 and Chemical Formula 2.

[0025] The metal adhesion improvement composition for the semiconductor process may further include an organic solvent.

[0026] The polymer including structural units represented by Chemical Formula 1 and Chemical Formula 2 may be included in an amount of about 0.1 wt % to about 10 wt % based on a total amount of the metal adhesion improvement composition including the organic solvent.

[0027] The polymer including structural units represented by Chemical Formula 1 and Chemical Formula 2 may be included in an amount of about 1 wt % to about 5 wt % based on a total amount of the metal adhesion improvement composition including the organic solvent.

[0028] A method for manufacturing a metal adhesion improvement composition for the semiconductor process according to one aspect includes forming a copolymer by copolymerizing a monomer represented by Chemical Formula 4 and a monomer represented by Chemical Formula 5; and adding the copolymer to an organic solvent.

[0029] In Chemical Formula 4 and Chemical Formula 5,

[0030] R1 is a substituted or unsubstituted C1 to C20 alkyl group,

[0031] L1 is a single bond, a substituted or unsubstituted C1 to C20 alkylene group, *—C(═O)NH—*, or *—O—*, and

[0032] L2 is a single bond or a substituted or unsubstituted C1 to C20 alkylene group.

[0033] The copolymer may include the structural unit represented by Chemical Formula 3.

[0034] The copolymer may include a structural unit represented by Chemical Formula 3-1.

[0035] The metal patterning method according to one aspect includes coating an adhesion improvement layer on a metal layer using a metal adhesion improvement composition for a semiconductor process including the polymer of a specific structure before applying an organic mask thereto, so that even if an organic mask with insufficient resistance to wet etching is used, wet etching patterning of the metal layer can be more easily performed, and even when an organic mask with comparatively excellent resistance to wet etching is used, the resistance to wet etching of the organic mask can be further enhanced.BRIEF DESCRIPTION OF THE DRAWINGS

[0036] The above and other aspects and features of the present disclosure will become more apparent by describing in detail exemplary embodiments thereof with reference to the attached drawings, in which:

[0037] FIG. 1 is a drawing sequentially showing a metal patterning method according to one aspect including dry and wet etching processes during a semiconductor process.

[0038] FIG. 2 is a drawing sequentially showing a metal patterning method including dry and wet etching processes among conventional semiconductor processes.

[0039] FIG. 3 is a photograph showing the spacing between gate metal layers after patterning the metal layers using the metal patterning method according to Example 1.

[0040] FIG. 4 is a photograph showing the spacing between gate metal layers before patterning the metal layers using the metal patterning method according to Example 1.

[0041] FIG. 5 is an XPS (X-ray Photoelectron Spectroscopy) graph when the coating conditions (heating temperature during coating, etc.) of the adhesion improvement layer are changed during patterning of the metal layer by a metal patterning method according to one aspect.

[0042] FIG. 6 is a photograph for confirming whether metal remains in a portion that is covered with an organic mask and a portion that is not covered after patterning a metal layer using the metal patterning method according to Example 1.

[0043] FIG. 7 is a photograph for confirming whether metal remains in a portion that is covered with an organic mask and a portion that is not covered after patterning a metal layer using the metal patterning method according to Comparative Example 1.DETAILED DESCRIPTION OF THE EMBODIMENTS

[0044] The present invention will be described more fully hereinafter with reference to the accompanying drawings, in which example embodiments of the invention are shown. As those skilled in the art would realize, the described embodiments may be modified in various different ways, all without departing from the spirit or scope of the present invention.

[0045] The drawings and description are to be regarded as illustrative in nature and not restrictive. Like reference numerals designate like elements throughout the specification.

[0046] The size and thickness of each constituent element as shown in the drawings are provided for better understanding and ease of description, and the disclosure is not necessarily limited to as shown. In the drawings, the thickness of layers, films, panels, regions, etc., may be exaggerated for clarity. In addition, in the drawings, for better understanding and ease of description, the thickness of some layers and areas may be exaggerated. Additionally, when the terms “about” or “substantially” are used in this specification in connection with a numerical value and / or geometric terms, it is intended that the associated numerical value includes a manufacturing tolerance (e.g., ±10%) around the stated numerical value. Further, regardless of whether numerical values and / or geometric terms are modified as “about” or “substantially,” it will be understood that these values should be construed as including a manufacturing or operational tolerance (e.g., ±10%) around the stated numerical values and / or geometric. When referring to “C to D”, this means C inclusive to D inclusive unless otherwise specified.

[0047] It will be understood that when an element such as a layer, film, region, or substrate is referred to as being “on” another element, it can be directly on the other element or intervening elements may also be present. In contrast, when an element is referred to as being “directly on” another element, there are no intervening elements present. Additionally, the word “on” or “above” means being disposed on or below the object portion, and does not necessarily mean being disposed on the upper side of the object portion based on a gravitational direction. More specifically, it will be understood that such spatially relative terms, such as “above”, “top”, etc., are intended to encompass different orientations of the device in use or operation in addition to the orientation depicted in the figures, and that the device may be otherwise oriented (rotated 90 degrees or at other orientations) and the spatially relative terms used herein interpreted accordingly.

[0048] In addition, unless explicitly described to the contrary, the word “comprise”, and variations such as “comprises” or “comprising”, will be understood to imply the inclusion of stated elements but not the exclusion of any other elements.

[0049] In addition, throughout the specification, when referring to “plane,” it means when the target part is viewed from above, and when referring to “cross section,” it means when viewing the cross section of the target portion vertically cut from the side.

[0050] The present disclosure relates to a metal patterning method of further enhancing resistance to wet etching of an organic mask for wet etching, which is used in the metal patterning process during the semiconductor process, and / or easing a metal patterning process with an organic mask with insufficient resistance to wet etching, which is not used in a conventional semiconductor process, a metal adhesion improvement composition for a semiconductor process used in the metal patterning method, and a method for manufacturing the same and in particular, after depositing a metal layer on a substrate but before applying an organic mask, applying the metal adhesion improvement composition for a semiconductor process on the metal layer and then, heating it to form an adhesion improvement layer thereon. Accordingly, the metal patterning process including the wet etching process may offer a wide range of available organic mask options and also, enhance resistance to wet etching of an organic mask, resulting in having an effect of increasing a patterning margin. In other words, through the adhesion improvement layer coating according to one aspect, in all layers requiring wet etching patterning, the wet etching patterning may not only be easily performed, but also, even if an organic mask with insufficient wet etching resistance is used, because wet etching resistance of the organic mask is enhanced, there may be an effect of improving a wet etching patterning process margin.

[0051] Conventionally, in order to prevent or reduce peeling between an organic mask and a metal layer, after enhancing resistance to wet etching of an organic mask by separately adding an additive for improving adhesion, for example, an aromatic compound (monomer) to the organic mask, the organic mask with enhanced resistance to wet etching is used to proceed with metal patterning, wherein there is a problem of limiting available types of organic mask according to the use of only an organic mask with enhanced resistance to wet etching. In addition, the addition of the additive for improving adhesion may bring about another problem of slowing down an etching rate during the dry etching.

[0052] Specifically, conventionally, when a scheme of coating an organic mask directly on a metal to be patterned and performing metal patterning is used, the conventional organic mask is not suited to perform the metal patterning due to insufficient resistance to wet etching (refer to FIG. 2), which may result in unwanted etching, such as under-etching. However, an adhesion improvement layer, if coated before coating an organic mask, may enhance resistance to wet etching of the organic mask, resulting in making it possible to use the conventional organic mask.

[0053] That is, as shown in FIG. 1, by applying an organic mask after performing an adhesion improvement layer coating, it is possible to manufacture a metal layer with excellent patternability even when using a conventional organic mask.

[0054] In other words, a metal patterning method according to one aspect includes depositing a metal layer on a substrate; coating an adhesion improvement layer on the metal layer; applying an organic mask on the adhesion improvement layer; performing exposing and etching; and removing the organic mask and adhesion improvement layer, wherein the coating of the adhesion improvement layer on the metal layer includes coating a metal adhesion improvement composition for a semiconductor process, which will be described later, on the metal layer and heating.

[0055] Referring to FIG. 1, in at least some embodiments, after coating the adhesion improvement layer onto the metal layer, a strip process may be further included before applying an organic mask.

[0056] Referring to FIG. 1, performing the exposing and etching may include exposing (or developing) a region of the organic mask such that a portion of the organic mask is reacted (e.g., cross-polymerized); dry etching after the exposure such that a region of the organic mask is removed and a region (corresponding to a desired pattern) remains; and performing wet etching after the dry etching such that the metal layer exposed by the dry etching is removed. In at least some embodiments, the exposing may include exposing regions of the organic mask to light, such that a photo-sensitive reaction occurs. In general, in the case of dry etching, electrical energy is applied to cause a reaction of an etching gas, converting the etching gas into a plasma state, and then the ions generated at this time are used to cause an etching reaction, e.g., with undeveloped regions of the organic mask. Since the ions travel in a straight line, anisotropic etching is performed in which etching is performed only in the vertical direction, so there is little to no concern about etching defects. However, in the case of wet etching, since the etching reaction is performed using an etchant, isotropic etching is performed in which etching is performed in both the horizontal and vertical directions, so there is a very high concern about etching defects occurring (see the wet etch portion of FIG. 2). However, since the metal patterning method according to one aspect includes coating an adhesion improvement layer on a metal layer before the exposing and etching steps and then applies an organic mask and then performing the exposing and etching process, the occurrence of etching defects can be significantly suppressed even in a wet etching process in which isotropic etching is performed.

[0057] After coating the metal adhesion improvement composition for the semiconductor process on the metal layer, heating is performed for coating. For example, the heating may be performed at about 100° C. to about 200° C., for example, about 110° C. to about 180° C. In at least some embodiments, if the heating is not performed, there is a risk that the coating will not be performed well and the metal patterning will proceed without forming an adhesion improvement layer. However, when the heating temperature exceeds about 200° C., there is no significant difference in the coating properties compared to when heating at a lower temperature, for example, a temperature of about 100° C. to about 200° C. More specifically, since there is a concern that the coating property may deteriorate when the heating temperature is lower than about 100° C., the heating temperature may be controlled to about 100° C. to about 200° C., for example, about 110° C. to about 180° C.

[0058] In at least some examples, the metal layer may include at least one of TiN, AlO, LaO, and / or a combination thereof.

[0059] In at least some examples, the organic mask may be an organic mask with enhanced resistance to wet etching, including, for example, a catechol-based compound.

[0060] Alternatively, in at least some examples, the organic mask may be a catechol-based compound-free organic mask that does not include a catechol-based compound and has poor resistance to wet etching.

[0061] The catechol-based compound may include a catechol compound and / or a derivative thereof.

[0062] Meanwhile, the metal adhesion improvement composition for the semiconductor process includes a polymer including structural units represented by Chemical Formula 1 and Chemical Formula 2.

[0063] In Chemical Formula 1 and Chemical Formula 2,

[0064] R1 is a substituted or unsubstituted C1 to C20 alkyl group,

[0065] L1 is a single bond, a substituted or unsubstituted C1 to C20 alkylene group, *—C(═O)NH—*, or *—O—*, and

[0066] L2 is a single bond or a substituted or unsubstituted C1 to C20 alkylene group. In at least some examples, when one of L1 or L2 is a single bond, the other is not a single bond.

[0067] Since the metal adhesion improvement composition for the semiconductor process includes the polymer including structural units represented by Chemical Formula 1 and Chemical Formula 2, the adhesion improvement coating layer has excellent adhesion to the metal layer, and thus can exhibit the above-described effect.

[0068] For example, the structural unit represented by Chemical Formula 1 enables the lowering of the glass transition temperature of the metal adhesion improvement composition for the semiconductor process, and the structural unit represented by Chemical Formula 2 enables the improving of the resistance to wet etching of the metal adhesion improvement composition for the semiconductor process, ultimately improving the resistance to wet etching of the organic mask. If the glass transition temperature of the metal adhesion improvement composition for the semiconductor process is high, the gap fill ability for filling fine gaps is deteriorated, making it difficult, if not impossible, to cover fine gaps with an adhesion improvement coating layer. In addition, if the resistance to wet etching of the metal adhesion improvement composition for the semiconductor process is inferior, there is a concern that the metal layer in the area covered with the organic mask may be partially and / or completely lost when the wet etching process is performed, thereby resulting in etching occurring in unwanted areas. That is, the polymer included in the metal adhesion improvement composition for the semiconductor process must include both the structural unit represented by Chemical Formula 1 and the structural unit represented by Chemical Formula 2. If it does not include either of these, the adhesion improvement coating layer is not properly coated on the metal layer and / or the effect of improving resistance to wet etching is not achieved.

[0069] In at least some examples, the structural unit represented by Chemical Formula 1 and the structural unit represented by Chemical Formula 2 may be included in a molar ratio of about 1:9 to about 9:1.

[0070] In at least some examples, Chemical Formula 2 may be represented by Chemical Formula 2-1 and / or Chemical Formula 2-2. In these cases, the coating properties of the adhesion improvement coating layer for the metal layer can be further enhanced, and the effect of improving resistance to wet etching can be considered to be very excellent.

[0071] In Chemical Formula 2-1 and Chemical Formula 2-2,

[0072] L1 is a single bond, a substituted or unsubstituted C1 to C20 alkylene group, *—C(═O)NH—*, or *—O—*, and

[0073] L2 is a single bond or a substituted or unsubstituted C1 to C20 alkylene group.

[0074] For example, the polymer may include a structural unit represented by Chemical Formula 3.

[0075] In Chemical Formula 3,

[0076] R1 is a substituted or unsubstituted C1 to C20 alkyl group,

[0077] L1 is a single bond, a substituted or unsubstituted C1 to C20 alkylene group, *—C(═O)NH—*, or *—O—*,

[0078] L2 is a single bond or a substituted or unsubstituted C1 to C20 alkylene group, and n:m=1:9 to 9:1.

[0079] For example, in Chemical Formula 1 to Chemical Formula 3, R1 may be an unsubstituted C1 to C10 alkyl group, L1 may be *—C(═O)NH—*, and L2 may be a substituted or unsubstituted C1 to C20 alkylene group, In these cases.

[0080] In at least some examples, in Chemical Formula 3, n: m may be 5:5 to 9:1. In these cases, since the structural unit represented by Chemical Formula 2 is included in a relatively larger amount than the structural unit represented by Chemical Formula 1, the above-described effect can be further increased.

[0081] For example, Chemical Formula 3 may be represented by Chemical Formula 3-1.

[0082] For example, the polymer may have a weight average molecular weight of about 3000 g / mol to about 8000 g / mol. When the weight average molecular weight of the polymer is within the above range, the effect of improving adhesion to the metal layer may be further doubled.

[0083] For example, the metal adhesion improvement composition for the semiconductor process may further include an organic solvent. At this time, the organic solvent is not particularly limited in type. For example, the organic solvent may be selected based on compatibility and reactivity with the other elements in the process, and may include, e.g., alcohols such as methanol, ethanol, and / or the like; ethers such as dichloroethyl ether, n-butyl ether, diisoamyl ether, methylphenyl ether, tetrahydrofuran, and / or the like; glycol ethers such as ethylene glycol monomethylether, ethylene glycol monoethylether, and / or the like; cellosolve acetates such as methyl cellosolve acetate, ethyl cellosolve acetate, diethyl cellosolve acetate, and / or the like; carbitols such as methylethyl carbitol, diethyl carbitol, diethylene glycol monomethylether, diethylene glycol monoethylether, diethylene glycol dimethylether, diethylene glycol methylethylether, diethylene glycol diethylether, and / or the like; propylene glycol alkylether acetates such as propylene glycol methylether acetate, propylene glycol propylether acetate, and / or the like; aromatic hydrocarbons such as toluene, xylene and / or the like; ketones such as methylethylketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, methyl-n-propylketone, methyl-n-butylketone, methyl-n-amylketone, 2-heptanone, and / or the like; saturated aliphatic monocarboxylic acid alkyl esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, and / or the like; lactate esters such as methyl lactate, ethyl lactate, and / or the like; oxy acetic acid alkyl esters such as oxy methyl acetate, oxy ethyl acetate, butyl oxyacetate, and / or the like; alkoxy acetic acid alkyl esters such as methoxy methyl acetate, methoxy ethyl acetate, methoxy butyl acetate, ethoxy methyl acetate, ethoxy ethyl acetate, and / or the like; 3-oxy propionic acid alkyl esters such as 3-oxy methyl propionate, 3-oxy ethyl propionate, and / or the like; 3-alkoxy propionic acid alkyl esters such as 3-methoxy methyl propionate, 3-methoxy ethyl propionate, 3-ethoxy ethyl propionate, 3-ethoxy methyl propionate, and / or the like; 2-oxy propionic acid alkyl esters such as 2-oxy methyl propionate, 2-oxy ethyl propionate, 2-oxy propyl propionate, and / or the like; 2-alkoxy propionic acid alkyl esters such as 2-methoxy methyl propionate, 2-methoxy ethyl propionate, 2-ethoxy ethyl propionate, 2-ethoxy methyl propionate, and / or the like; 2-oxy-2-methyl propionic acid esters such 2-oxy-2-methyl methyl propionate, 2-oxy-2-methyl ethyl propionate, and / or the like, monooxy monocarboxylic acid alkyl esters of 2-alkoxy-2-methyl alkyl propionates such as 2-methoxy-2-methyl methyl propionate, 2-ethoxy-2-methyl ethyl propionate, and / or the like; esters such as 2-hydroxy ethyl propionate, 2-hydroxy-2-methyl ethyl propionate, hydroxy ethyl acetate, 2-hydroxy-3-methyl methyl butanoate, and / or the like; ketonate esters such as ethyl pyruvate, and / or the like. Additionally, high boiling point solvent such as N-methylformamide, N,N-dimethylformamide, N-methylformanilide, N-methylacetamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, benzylethylether, dihexylether, acetylacetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzylalcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, phenyl cellosolve acetate, and / or the like may be also used.

[0084] Among these, considering compatibility and reactivity, examples thereof include ketones such as cyclohexanone; glycol ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; ethylene glycol alkyl ether acetates such as ethyl cellosolve acetate; esters such as ethyl 2-hydroxypropionate; carbitols such as diethylene glycol monomethyl ether; and propylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate and propylene glycol propyl ether acetate.

[0085] For example, the polymer including structural units represented by Chemical Formula 1 and Chemical Formula 2 may be included in an amount of about 0.1 percent by weight (wt %) to about 10 wt %, for example about 1 wt % to about 5 wt % based on a total amount of the metal adhesion improvement composition including the organic solvent. When the polymer is included within the above range, the adhesion improvement composition for a semiconductor process can have an appropriate viscosity and thus have excellent processability during coating.

[0086] According to one aspect, a method for manufacturing the adhesion improvement composition for a semiconductor process is provided. Specifically, the method includes forming a copolymer by copolymerizing a monomer represented by Chemical Formula 4 and a monomer represented by Chemical Formula 5; and adding the copolymer to an organic solvent.

[0087] In Chemical Formula 4 and Chemical Formula 5,

[0088] R1 is a substituted or unsubstituted C1 to C20 alkyl group,

[0089] L1 is a single bond, a substituted or unsubstituted C1 to C20 alkylene group, *—C(═O)NH—*, or *—O—*, and

[0090] L2 is a single bond or a substituted or unsubstituted C1 to C20 alkylene group.

[0091] The monomer represented by Chemical Formula 4 may be copolymerized to form a structural unit represented by Chemical Formula 1, and the monomer represented by Chemical Formula 5 may be copolymerized to form a structural unit represented by Chemical Formula 2. In at least some examples, the copolymerization may include a chain growth polymerization reaction. Accordingly, the copolymer may include a structural unit represented by Chemical Formula 3, more specifically, a structural unit represented by Chemical Formula 3-1.

[0092] Although the exemplary embodiments have been described above, they are not limited to the exemplary embodiments described above, and various additions, omissions, substitutions, and changes may be made. Additionally, it is possible to form other embodiments by combining elements in different embodiments.

[0093] Hereinafter, various experiments using a metal adhesion improvement composition for the semiconductor process according to an embodiment are described. The experiments described below do not limit the present disclosure.EXAMPLESSynthesis of PolymersSynthesis Example 1:

[0094] A polymer (a weight average molecular weight: 6000 g / mol) containing a structural unit represented by Chemical Formula 3-1 was synthesized by free radical polymerization (using AIBN as an initiator) of a butyl acrylate monomer and a dopamine monomer at 60° C.Synthesis Example 2:

[0095] A polymer (a weight average molecular weight: 4000 g / mol) containing a structural unit represented by Chemical Formula 3-2 was synthesized in the same manner as in Synthesis Example 1 except that contents of the butyl acrylate monomer and the dopamine monomer were changed.Synthesis Example 3:

[0096] A polymer (a weight average molecular weight: 7200 g / mol) containing a structural unit represented by Chemical Formula 3-3 was synthesized in the same manner as in Synthesis Example 1 except that contents of the butyl acrylate monomer and the dopamine monomer were changed.Synthesis Example 4:

[0097] A polymer (a weight average molecular weight: 8000 g / mol) containing a structural unit represented by Chemical Formula 3-4 was synthesized in the same manner as in Synthesis Example 1 except that contents of the butyl acrylate monomer and the dopamine monomer were changed.Synthesis Example 5:

[0098] A polymer (a weight average molecular weight: 3000 g / mol) containing a structural unit represented by Chemical Formula 3-5 was synthesized in the same manner as in Synthesis Example 1 except that contents of the butyl acrylate monomer and the dopamine monomer were changed.Synthesis Example 6:

[0099] A polymer (a weight average molecular weight: 8400 g / mol) containing a structural unit represented by Chemical Formula 3-6 was synthesized in the same manner as in Synthesis Example 1 except that contents of the butyl acrylate monomer and the dopamine monomer were changed.Synthesis Example 7:

[0100] A polymer (a weight average molecular weight: 2800 g / mol) containing a structural unit represented by Chemical Formula 3-7 was synthesized in the same manner as in Synthesis Example 1 except that contents of the butyl acrylate monomer and the dopamine monomer were changed.Synthesis Example 8:

[0101] A polymer (a weight average molecular weight: 6600 g / mol) containing a structural unit represented by Chemical Formula 3-8 was synthesized in the same manner as in Synthesis Example 1 except that 2-ethylhexylacrylate was used instead of the butyl acrylate monomer.Synthesis Example 9:

[0102] A polymer (a weight average molecular weight: 8700 g / mol) containing a structural unit represented by Chemical Formula 3-9 was synthesized in the same manner as in Synthesis Example 1 except that a stearyl acrylate monomer was used instead of the butyl acrylate monomer.Synthesis Example 10:

[0103] A polymer (a weight average molecular weight: 6000 g / mol) containing a structural unit represented by Chemical Formula 3-10 was synthesized in the same manner as in Synthesis Example 1 except that types of the dopamine monomer was changed.Comparative Synthesis Example 1:

[0104] A polymer was synthesized in the same manner as in Synthesis Example 1 except that the dopamine monomer was not used.Comparative Synthesis Example 2:

[0105] A polymer was synthesized in the same manner as in Synthesis Example 1 except that the butyl acrylate monomer was not used.Preparation of Metal Adhesion Improvement Composition for Semiconductor ProcessPreparation Example 1-1:

[0106] A metal adhesion improvement composition for a semiconductor process was prepared by dissolving the polymer of Synthesis Example 1 in a PGME solvent to be 4 wt % based on the total composition.Preparation Example 1-2:

[0107] A metal adhesion improvement composition for a semiconductor process was prepared by dissolving the polymer of Synthesis Example 1 in a PGME solvent to be 0.1 wt % based on the total composition.Preparation Example 1-3:

[0108] A metal adhesion improvement composition for a semiconductor process was prepared by dissolving the polymer of Synthesis Example 1 in a PGME solvent to be 0.05 wt % based on the total composition.Preparation Example 1-4:

[0109] A metal adhesion improvement composition for a semiconductor process was prepared by dissolving the polymer of Synthesis Example 1 in a PGME solvent to be 1 wt % based on the total composition.Preparation Example 1-5:

[0110] A metal adhesion improvement composition for a semiconductor process was prepared by dissolving the polymer of Synthesis Example 1 in a PGME solvent to be 7 wt % based on the total composition.Preparation Example 1-6:

[0111] A metal adhesion improvement composition for a semiconductor process was prepared by dissolving the polymer of Synthesis Example 1 in a PGME solvent to be 10 wt % based on the total composition.Preparation Example 1-7:

[0112] A metal adhesion improvement composition for a semiconductor process was prepared by dissolving the polymer of Synthesis Example 1 in a PGME solvent to be 11 wt % based on the total composition.Preparation Example 2:

[0113] A metal adhesion improvement composition for a semiconductor process was prepared in the same manner as in Preparation Example 1 except that the polymer of Synthesis Example 2 was used instead of the polymer of Synthesis Example 1.Preparation Example 3:

[0114] A metal adhesion improvement composition for a semiconductor process was prepared in the same manner as in Preparation Example 1 except that the polymer of Synthesis Example 3 was used instead of the polymer of Synthesis Example 1.Preparation Example 4:

[0115] A metal adhesion improvement composition for a semiconductor process was prepared in the same manner as in Preparation Example 1 except that the polymer of Synthesis Example 4 was used instead of the polymer of Synthesis Example 1.Preparation Example 5:

[0116] A metal adhesion improvement composition for a semiconductor process was prepared in the same manner as in Preparation Example 1 except that the polymer of Synthesis Example 5 was used instead of the polymer of Synthesis Example 1.Preparation Example 6:

[0117] A metal adhesion improvement composition for a semiconductor process was prepared in the same manner as in Preparation Example 1 except that the polymer of Synthesis Example 6 was used instead of the polymer of Synthesis Example 1.Preparation Example 7:

[0118] A metal adhesion improvement composition for a semiconductor process was prepared in the same manner as in Preparation Example 1 except that the polymer of Synthesis Example 7 was used instead of the polymer of Synthesis Example 1.Preparation Example 8:

[0119] A metal adhesion improvement composition for a semiconductor process was prepared in the same manner as in Preparation Example 1 except that the polymer of Synthesis Example 8 was used instead of the polymer of Synthesis Example 1.Preparation Example 9:

[0120] A metal adhesion improvement composition for a semiconductor process was prepared in the same manner as in Preparation Example 1 except that the polymer of Synthesis Example 9 was used instead of the polymer of Synthesis Example 1.Preparation Example 10:

[0121] A metal adhesion improvement composition for a semiconductor process was prepared in the same manner as in Preparation Example 1 except that the polymer of Synthesis Example 10 was used instead of the polymer of Synthesis Example 1.Comparative Preparation Example 1:

[0122] A metal adhesion improvement composition for a semiconductor process was prepared in the same manner as in Preparation Example 1 except that the polymer of Comparative Synthesis Example 1 was used instead of the polymer of Synthesis Example 1.Comparative Preparation Example 2:

[0123] A metal adhesion improvement composition for a semiconductor process was prepared in the same manner as in Preparation Example 1 except that the polymer of Comparative Synthesis Example 2 was used instead of the polymer of Synthesis Example 1.Metal PatterningExample 1

[0124] After depositing TiN on a substrate, the composition of Preparation Example 1-1 was coated on the TiN and then, heated at 110° C. to coat an adhesion improvement layer thereon. Subsequently, after applying an organic mask on the coated adhesion improvement layer exposure and etching proceeded, and lastly, the organic mask and the adhesion improvement layer were peeled off to perform TiN patterning.Example 2

[0125] TiN patterning proceeded in the same manner as in Example 1 except that the heating temperature for coating the adhesion improvement layer was changed from 110° C. to 180° C.Example 3: (Reference)

[0126] TiN patterning proceeded in the same manner as in Example 1 except that the heating temperature for coating the adhesion improvement layer was changed from 110° C. to 90° C.Example 4: (For Reference Only)

[0127] TiN patterning proceeded in the same manner as in Example 1 except that the composition of Preparation Example 1-2 was used instead of the composition of Preparation Example 1-1.Example 5: (Reference)

[0128] TiN patterning proceeded in the same manner as in Example 1 except that the composition of Preparation Example 1-3 was used instead of the composition of Preparation Example 1-1.Example 6

[0129] TiN patterning proceeded in the same manner as in Example 1 except that the composition of Preparation Example 1-4 was used instead of the composition of Preparation Example 1-1.Example 7

[0130] TiN patterning proceeded in the same manner as in Example 1 except that the composition of Preparation Example 1-5 was used instead of the composition of Preparation Example 1-1.Example 8: (For Reference)

[0131] TiN patterning proceeded in the same manner as in Example 1 except that the composition of Preparation Example 1-6 was used instead of the composition of Preparation Example 1-1.Example 9: (For Reference)

[0132] TiN patterning proceeded in the same manner as in Example 1 except that the composition of Preparation Example 1-7 was used instead of the composition of Preparation Example 1-1.Example 10

[0133] TiN patterning proceeded in the same manner as in Example 1 except that the composition of Preparation Example 2 was used instead of the composition of Preparation Example 1-1.Example 11

[0134] TiN patterning proceeded in the same manner as in Example 1 except that the composition of Preparation Example 3 was used instead of the composition of Preparation Example 1-1.Example 12

[0135] TiN patterning proceeded in the same manner as in Example 1 except that the composition of Preparation Example 4 was used instead of the composition of Preparation Example 1-1.Example 13

[0136] TiN patterning proceeded in the same manner as in Example 1 except that the composition of Preparation Example 5 was used instead of the composition of Preparation Example 1-1.Example 14: (For Reference)

[0137] TiN patterning proceeded in the same manner as in Example 1 except that the composition of Preparation Example 6 was used instead of the composition of Preparation Example 1-1.Example 15: (For Reference)

[0138] TiN patterning proceeded in the same manner as in Example 1 except that the composition of Preparation Example 7 was used instead of the composition of Preparation Example 1-1.Example 16

[0139] TiN patterning proceeded in the same manner as in Example 1 except that the composition of Preparation Example 8 was used instead of the composition of Preparation Example 1-1.Example 17: (For Reference)

[0140] TiN patterning proceeded in the same manner as in Example 1 except that the composition of Preparation Example 9 was used instead of the composition of Preparation Example 1-1.Example 18

[0141] TiN patterning proceeded in the same manner as in Example 1 except that the composition of Preparation Example 10 was used instead of the composition of Preparation Example 1-1.Comparative Example 1

[0142] TiN patterning proceeded in the same manner as in Example 1 except that the adhesion improvement layer was not formed by coating the composition of Preparation Example 1-1.Comparative Example 2

[0143] TiN patterning proceeded in the same manner as in Example 1 except that the composition of Comparative Preparation Example 1 was used instead of the composition of Preparation Example 1-1.Comparative Example 3

[0144] TiN patterning proceeded in the same manner as in Example 1 except that the composition of Comparative Preparation Example 2 was used instead of the composition of Preparation Example 1-1.Comparative Example 4

[0145] TiN patterning proceeded in the same manner as in Example 1 except that the heating process for coating the adhesion improvement layer was not performed.(Evaluation 1)

[0146] In the metal layers (TiN) patterned according to the methods according to Examples 1 to 18 and Comparative Examples 1 to 4, after depositing each of the metal layers on a substrate, a thickness (gap) between the metal layers was checked, and subsequently, after coating an adhesion improvement layer thereon and performing a peeling process by using an ArF thinner (up to the strip process of FIG. 1), the thickness (gap) between the metal layers was checked again, and the results are shown in Tables 1 to 3 and FIGS. 3 and 4. Referring to Table 1 and FIGS. 3 and 4. in the metal layer patterned in the method of Example 1. the adhesion improvement layer was respectively coated to have a thickness of 2 nm on the metal layer.TABLE 1(unit: nm)Examples123456789Gap before coating adhesion161616161616161616improvement layerGap after coating adhesion121214131412121314improvement layerTABLE 2(unit: nm)Examples101112131415161718Gap before coating adhesion161616161616161616improvement layerGap after coating adhesion121212121414121412improvement layerTABLE 3(unit: nm)ComparativeComparativeComparativeComparativeExample 1Example 2Example 3Example 4Gap before coating16161616adhesion improvementlayerGap after coating—151516adhesion improvementlayerReferring to Table 3, in Comparative Example 1, which had no adhesion improvement layer coating, there was no gap data after the adhesion improvement layer coating, and in Comparative Examples 2 to 4, the adhesion improvement layer was almost not coated.(Evaluation 2)After coating the adhesion improvement layer in Example 1, Example 2, Comparative Examples 1 and 4 of Evaluation 1 and performing the peeling process by using an ArF thinner (up to the strip process of FIG. 1), the metal layer patterns were subjected to XPS analysis, and the results are shown in FIG. 5.

[0149] Referring to FIG. 5, through XPS, it was confirmed that after the adhesion improvement layer coating, a Ti peak decreased, but a C═O peak of the adhesion improvement layer increased and in particular, became saturated from a temperature of 110° C. or more. In other words, in order to coat an adhesion improvement composition for a semiconductor process on a metal layer on a substrate, a heating process is necessary to perform, and the heating temperature of 110° C. or higher was confirmed to be sufficient for the heating process.(Evaluation 3)

[0150] The metal layers (TiN) respectively patterned in the methods according to Examples 1 to 18 and Comparative Examples 1 to 4 were taken a scanning electron microscope (SEM) image of to check whether TiN was present or not in a region (wet block) covered with an organic mask, and the results are shown in Tables 4 to 6 and FIGS. 6 and 7. In Tables 4 to 6, if TiN was confirmed on a scanning electron microscope image, ○ was given, but if not confirmed, X was given. Referring to Tables 4 and 6 and FIGS. 6 and 7, the metal layer patterned in the method of Example 1 exhibited that TIN was present in the region covered with the organic mask, but the metal layer patterned in the method of Comparative Example 1 exhibited that TiN was all lost equally even in the region covered with the organic mask like in the region (wet open) not covered with the organic mask.TABLE 4Examples123456789Presence or absence of TiN◯◯X◯X◯◯◯Xin the region covered withorganic maskTABLE 5Examples101112131415161718Presence or absence of TiN◯◯◯◯XX◯X◯in the region covered withorganic maskTABLE 6ComparativeComparativeComparativeComparativeExample 1Example 2Example 3Example 4Presence or absence ofXXXXTiN in the regioncovered with organicmaskWhile this invention has been described in connection with what is presently considered to be practical exemplary embodiments, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims.

Examples

synthesis example 1

[0094]A polymer (a weight average molecular weight: 6000 g / mol) containing a structural unit represented by Chemical Formula 3-1 was synthesized by free radical polymerization (using AIBN as an initiator) of a butyl acrylate monomer and a dopamine monomer at 60° C.

synthesis example 2

[0095]A polymer (a weight average molecular weight: 4000 g / mol) containing a structural unit represented by Chemical Formula 3-2 was synthesized in the same manner as in Synthesis Example 1 except that contents of the butyl acrylate monomer and the dopamine monomer were changed.

synthesis example 3

[0096]A polymer (a weight average molecular weight: 7200 g / mol) containing a structural unit represented by Chemical Formula 3-3 was synthesized in the same manner as in Synthesis Example 1 except that contents of the butyl acrylate monomer and the dopamine monomer were changed.

Claims

1. A metal patterning method, comprisingdepositing a metal layer on a substrate;coating an adhesion improvement layer on the metal layer;applying an organic mask on the adhesion improvement layer;etching the metal layer using the organic mask; andremoving the organic mask and adhesion improvement layer from the etched metal layer,wherein the coating of the adhesion improvement layer on the metal layer comprisescoating a metal adhesion improvement composition on the metal layer, andheating the metal adhesion improvement composition,wherein the metal adhesion improvement composition includes a polymer comprising structural units represented by Chemical Formula 1 and Chemical Formula 2wherein, in Chemical Formula 1 and Chemical Formula 2,R1 is a substituted or unsubstituted C1 to C20 alkyl group,L1 is a single bond, a substituted or unsubstituted C1 to C20 alkylene group, *—C(═O)NH—*, or *—O—*, andL2 is a single bond or a substituted or unsubstituted C1 to C20 alkylene group.

2. The metal patterning method of claim 1, whereinChemical Formula 2 is represented by at least one of Chemical Formula 2-1 or Chemical Formula 2-2:

3. The metal patterning method of claim 1, wherein the etching comprises:exposing the organic mask;dry etching the organic mask after the exposure such that regions of the organic mask are removed; andperforming wet etching after the dry etching.

4. The metal patterning method of claim 1, whereinthe polymer comprises a structural unit represented by Chemical Formula 3:wherein, in Chemical Formula 3, n:m=1:9 to 9:1.

5. The metal patterning method of claim 1, whereinR1 is the unsubstituted C1 to C10 alkyl group,L1 is the *—C(═O)NH—*, andL2 is the substituted or unsubstituted C1 to C20 alkylene group.

6. The metal patterning method of claim 1, whereinthe heating is performed at about 100° C. to about 200° C.

7. The metal patterning method of claim 1, whereinthe metal layer comprises TiN.

8. The metal patterning method of claim 1, whereinthe organic mask is a catechol-based compound-free mask.

9. A metal adhesion improvement composition comprising:a polymer including structural units represented by Chemical Formula 1 and Chemical Formula 2:wherein, in Chemical Formula 1 and Chemical Formula 2,R1 is a substituted or unsubstituted C1 to C20 alkyl group,L1 is a single bond, a substituted or unsubstituted C1 to C20 alkylene group, *—C(═O)NH—*, or *—O—*, andL2 is a single bond or a substituted or unsubstituted C1 to C20 alkylene group.

10. The metal adhesion improvement composition of claim 9, whereinChemical Formula 2 is represented by at least one of Chemical Formula 2-1 or Chemical Formula 2-2:

11. The metal adhesion improvement composition of claim 9, whereinthe polymer comprises a structural unit represented by Chemical Formula 3:wherein, in Chemical Formula 3, n:m=1:9 to 9:1.

12. The metal adhesion improvement composition of claim 11, wherein the n:m=5:5 to 9:1.

13. The metal adhesion improvement composition of claim 9, whereinR1 is the unsubstituted C1 to C10 alkyl group,L1 is the *—C(═O)NH—*, andL2 is the substituted or unsubstituted C1 to C20 alkylene group.

14. The metal adhesion improvement composition of claim 9, whereinthe polymer has a weight average molecular weight of about 3000 g / mol to about 8000 g / mol.

15. The metal adhesion improvement composition of claim 9, further comprises:an organic solvent.

16. The metal adhesion improvement composition of claim 15, wherein the polymer including structural units represented by Chemical Formula 1 and Chemical Formula 2 is included in an amount of about 0.1 wt % to about 10 wt % based on a total amount of the metal adhesion improvement composition including the organic solvent.

17. The metal adhesion improvement composition of claim 16, wherein the amount of the polymer including structural units represented by Chemical Formula 1 and Chemical Formula 2 is of about 1 wt % to about 5 wt % based on the total amount of the metal adhesion improvement composition including the organic solvent.

18. A method for manufacturing a metal adhesion improvement composition for a semiconductor process, comprisingforming a copolymer by copolymerizing a monomer represented by Chemical Formula 4 and a monomer represented by Chemical Formula 5; andadding the copolymer to an organic solvent:wherein, in Chemical Formula 4 and Chemical Formula 5,R1 is a substituted or unsubstituted C1 to C20 alkyl group,L1 is a single bond, a substituted or unsubstituted C1 to C20 alkylene group, *—C(═O)NH—*, or *—O—*, andL2 is a single bond or a substituted or unsubstituted C1 to C20 alkylene group.

19. The method of claim 18, whereinthe copolymer comprises a structural unit represented by Chemical Formula 3:wherein, in Chemical Formula 3, n:m=1:9 to 9:1.

20. The method of claim 19, whereinthe copolymer comprises a structural unit represented by Chemical Formula 3-1:

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