Metal-containing photoresist developer composition, and pattern forming method including a development step using the same

Abstract

Providing a developer composition for a metal-containing photoresist, etc. 【Solution means】For the first photoresist exposed with a first exposure energy of 9 to 12 mJ / cm 2 Coordinate a specified by the Hansen solubility parameter of the first photoresist; for the metal-containing photoresist, with respect to the first exposure energy, a second exposure energy increased by 5 to 10 mJ / cm 2 Coordinate b specified by the Hansen solubility parameter of the second photoresist exposed with the increased second exposure energy; and for coordinate x specified by the Hansen solubility parameter of the developer composition, a solubility radius R with a and b as the central values a and R b are calculated, and for the distance (x, a) between x and a and the distance (x, b) between x and b according to Equation 1, (x, a) < R a and (x, b) > R b A developer composition in which the relationship holds: <Equation 1> (x, a) 2 = 4(δd x - δd a ) 2 +(δp x - δp a ) 2 +(δh x - δh a ) 2 (x, b) 2 = 4(δd x - δd b ) 2 +(δp x - δp b ) 2 +(δh x - δh b ) 2

Description

[Technical Field]

[0001] This description relates to a metal-containing photoresist developer composition and a pattern formation method including a development step using the same. [Background technology]

[0002] Recently, the semiconductor industry has seen a continuous reduction in critical dimensions, and this reduction in dimensions has led to a demand for new types of high-performance photoresist materials and patterning methods to meet the requirements for processing and patterning increasingly smaller features.

[0003] Traditional chemically amplified (CA) photoresists, while designed for high sensitivity, can be problematic under EUV exposure, partly due to their typical elemental makeup (primarily C with smaller quantities of O, F, and S) which lowers the absorbance of the photoresist at a wavelength of 13.5 nm, resulting in reduced sensitivity. CA photoresists can also be problematic due to roughness issues at small feature sizes, and experimentally, the LER has been shown to increase due to a decrease in photospeed, partly due to the nature of the acid-catalyzed process. Due to the shortcomings and problems of CA photoresists, the semiconductor industry has a demand for a new type of high-performance photoresist.

[0004] In particular, there is a need to develop photoresists that can ensure excellent etching resistance and resolution in the photolithography process, while simultaneously improving sensitivity and CD (critical dimension) uniformity, and thus improving LER (line edge roughness) characteristics. [Overview of the project] [Problems that the invention aims to solve]

[0005] One embodiment provides a developer composition for a metal-containing photoresist.

[0006] Another embodiment provides a patterning method including a developing step using the composition.

Means for Solving the Problems

[0007] The developer composition applied to a metal-containing photoresist according to one embodiment is coordinate a specified by the Hansen solubility parameters (δd, δp, δh) of the first photoresist exposed with the first exposure energy of 9 to 12 mJ / cm 2 ; coordinate b specified by the Hansen solubility parameters (δd, δp, δh) of the second photoresist exposed with the second exposure energy increased by 5 to 10 mJ / cm with respect to the first exposure energy; and 2 with respect to coordinate x specified by the Hansen solubility parameters (δd, δp, δh) of the developer composition, calculate a soluble radius R centered on the coordinate a, a calculate a soluble radius R centered on the coordinate b, b calculate, and for the distance (x, a) between coordinate x and coordinate a and the distance (x, b) between coordinate x and coordinate b calculated by the following formula 1 (x, a) < R a and (x, b) > R b the relationship holds.

[0008] <Formula 1> (x, a) 2 = 4(δd x - δd a ) 2 + (δp x - δp a ) 2 + (δh x - δh a ) 2 (x, b) 2 =4(δd x -δd b ) 2 +(δp x -δp b ) 2 +(δh x -δh b ) 2 (Hansen Solubility Parameter (HSP), solubility radius R) a and solubility radius R b (This was predicted using the Generate Hansen Parameters module of the COSMOquick22 version program.)

[0009] A pattern formation method according to another embodiment includes the steps of applying a metal-containing photoresist composition onto a substrate, a heat treatment step of drying and heating to form a metal-containing photoresist film on the substrate, an exposure step of the metal-containing photoresist film, and a development step of using the aforementioned metal-containing photoresist developer composition. [Effects of the Invention]

[0010] In one embodiment, a developer composition applied to a metal-containing photoresist can be derived through simulation to have a specific Hansen solubility parameter. By applying a developer composition that satisfies these parameters, the solubility of the unexposed areas is increased and the solubility of the exposed areas is decreased, improving the solubility ratio between the unexposed and exposed areas. This results in a photoresist pattern with significantly reduced scum and bridging while maintaining excellent sensitivity. [Brief explanation of the drawing]

[0011] [Figure 1] This is a cross-sectional view showing the process sequence to illustrate the pattern formation method. [Figure 2]This is a schematic diagram showing the solubility range of each photoresist based on exposure energy, obtained by performing a simulation on the composition according to the present invention. [Modes for carrying out the invention]

[0012] Embodiments of the present invention will be described in detail below with reference to the attached drawings. However, in order to clarify the gist of this description, descriptions of functions or configurations that have already been made public will be omitted.

[0013] To clearly explain this description, unnecessary explanatory parts have been omitted, and the same or similar components are given the same reference numerals throughout the specification. Furthermore, the dimensions and thicknesses of each component shown in the drawings are provided arbitrarily for explanatory purposes, and this description is not necessarily limited to those shown in the drawings.

[0014] In the drawings, the thicknesses were enlarged to clearly represent various layers and regions. Furthermore, for ease of explanation, the thicknesses of some layers and regions were exaggerated in the drawings. When a layer, film, region, plate, or other part is described as being "on top of" or "on" another part, this includes not only cases where it is "directly on top of" another part, but also cases where another part lies in between.

[0015] Here, the Hansen Solubility Parameter (HSP) is a value used to predict the solubility of a substance. The Hansen Solubility Parameter, also called the dissolving capacity of organic substances, reflects the physicochemical solubility properties. The HSP is based on the idea that "two substances with similar intermolecular interactions readily dissolve in each other." The Hansen Solubility Parameter can be calculated using an approach proposed by Charles Hansen in "Hansen Solubility Parameters: A user's handbook," Second Edition (2007), Boca Raton, Fla.: CRC Press, ISBN 978-0-8493-7248-3. According to this approach, three parameters called "Hansen parameters"—δd, δp, and δh—are sufficient to predict the behavior of a solvent for a given molecule. MPa 1 / 2 The parameter δd quantifies the energy of the dispersion force between molecules, i.e., the van der Waals force. MPa 1 / 2 The parameter δp represents the energy of the intermolecular bipolar interaction. Finally, MPa 1 / 2 The parameter δh quantifies the energy derived from intermolecular hydrogen bonding, i.e., the ability to interact through hydrogen bonding.

[0016] These three parameters can be considered as coordinates in three-dimensional space (Hansen space). When the HSPs of two substances are placed in Hansen space, the closer the distance between the two points, the easier they are to dissolve each other.

[0017] Since HSP is a vector quantity, it is known that very few pure substances have completely identical HSP values. Furthermore, databases have been established for commonly used substances. Therefore, those skilled in the art can obtain the HSP value of a desired substance by referring to these databases.

[0018] Even for substances whose HSP values ​​are not registered in the database, the HSP value can be calculated from their chemical structure using computer software such as COSMOqucik.

[0019] In other words, if the molecular smiles code is input as input data, the database value will be predicted if the molecular HSP exists in the COSMOquick DB, and if it does not exist in the DB, the HSP value of the molecular can be predicted using the system's own prediction formula.

[0020] The following describes a developer composition applicable to a metal-containing photoresist according to one embodiment.

[0021] A developing solution composition for a metal-containing photoresist according to one embodiment of the present invention allows the metal-containing photoresist to develop at a rate of 9 to 12 mJ / cm³. 2 Coordinate a, defined by the Hansen solubility parameters (δd, δp, δh) of the first photoresist exposed at the first exposure energy; The metal-containing photoresist is exposed to 5-10 mJ / cm² relative to the first exposure energy. 2 The coordinate b is identified by the Hansen solubility parameters (δd, δp, δh) of the second photoresist exposed with an increased second exposure energy; and For a coordinate x specified by the Hansen solubility parameters (δd, δp, δh) of the developer composition, The solubility radius R with coordinate a as its center value. a Calculate, The solubility radius R with coordinate b as its center value. b Calculate, For the distance between coordinate x and coordinate a (x, a) and the distance between coordinate x and coordinate b (x, b) calculated by the following formula 1, (x, a) <R a and (x, b) > R b The following relationship holds true.

[0022] <Expression 1> (x, a) 2 =4(δd x -δda ) 2 +(δp x -δp a ) 2 +(δh x -δh a ) 2 (x, b) 2 =4(δd x -δd b ) 2 +(δp x -δp b ) 2 +(δh x -δh b ) 2 (Hansen Solubility Parameter (HSP), solubility radius R) a and solubility radius R b (This was predicted using the Generate Hansen Parameters module of the COSMOquick22 version program.)

[0023] The Hansen solubility parameter (HSP) is an index that indicates the dispersion, polarity, and hydrogen bonding of a substance, and is useful for determining the compatibility between substances. It numerically represents the solubility between substances based on their dispersion force (δd), polarity force (δp), and hydrogen bonding force (δh), and coordinates each substance in three-dimensional space using the δd, δp, and δh factors as axes.

[0024] The photoresist being dissolved undergoes structural and chemical changes upon energy irradiation, and it can be understood that these changes also alter the solubility parameter. By classifying the changing solubility according to the energy irradiation dose and calculating the Hansen parameter through simulation, it is possible to compare how the positional value of the parameter changes depending on the structural state and composition of the material.

[0025] By coating a photoresist with energy to a certain thickness and then comparing the thickness after dissolving it using a developer solution composition, it is possible to determine whether or not it has dissolved.

[0026] On the other hand, each substance has its own unique solubility radius (R a , R b By determining the distance between the two components {(x, a) and (x, b)}, the solubility between the two components can be quantified.

[0027] In this case, the smaller the distance {(x, a) and (x, b)} between the two components in space, the more compatible they are with each other, that is, the higher their solubility.

[0028] Figure 2 is a schematic diagram showing the solubility range of each photoresist based on exposure energy, obtained by performing a simulation on the composition according to the present invention.

[0029] Referring to Figure 2, the region with high solubility in the unexposed area is <1> and <4> The display shows that the region with high solubility in the exposed area is <2> and <4> This is what is displayed.

[0030] At this time, the solubility in the unexposed areas is high, but the solubility in the exposed areas is low, and there is a region where the difference in solubility between the unexposed and exposed areas is clearly contrasted. <1> This is the area where it is displayed, and the developer composition to be realized in this invention is as described above. <1> It has parameters in the area that are displayed as follows: <2> , <3> , and <4> The region is as described above <1> These can be defined as regions where sensitivity decreases or where scum and bridging occur in contrast to other regions.

[0031] On the other hand, domain <3> This refers to a region where solubility is low in both the unexposed and exposed areas.

[0032] An example of a metal-containing photoresist developer composition according to one embodiment may include, but is not limited to, at least one of ethers, alcohols, glycol ethers, aromatic hydrocarbon compounds, ketones, and esters.For example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol methyl ether, diethylene glycol ethyl ether, propylene glycol, propylene glycol methyl ether (PGME), propylene glycol methyl ether acetate (PGMEA), propylene glycol ethyl ether, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, propylene glycol butyl ether, propylene glycol butyl ether acetate, ethanol, propanol, isopropyl alcohol, isobutyl alcohol, 2-butanol, 4-methyl-2-pentanol (or methyl isobutyl Carbinol (MIBC) can be written as, hexanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, ethylene glycol, propylene glycol, heptanone, propylene carbonate, butylene carbonate, toluene, xylene, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-heptanone, acetylacetone, acetic acid, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate This may include, but is not limited to, pyruvate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, gamma-butyrolactone, methyl 2-hydroxyisobutyrate, methoxybenzene, n-butyl acetate, 1-methoxy-2-propyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, or mixtures thereof.

[0033] The metal-containing photoresist developer composition according to the present invention may further contain at least one other additive selected from organic acids, surfactants, dispersants, hygroscopic agents, and coupling agents.

[0034] On the other hand, according to another embodiment, a pattern forming method can be provided that includes a development step using the aforementioned metal-containing photoresist developer composition. For example, the manufactured pattern may be a negative-type photoresist pattern.

[0035] A pattern formation method according to one embodiment includes the steps of: applying a metal-containing photoresist composition onto a substrate; performing a heat treatment step of drying and heating to form a metal-containing photoresist film on the substrate; exposing the metal-containing photoresist film to light; and developing the film using the aforementioned metal-containing photoresist developer composition.

[0036] More specifically, the step of forming a pattern using a metal-containing photoresist composition may include the steps of applying the metal-containing photoresist composition onto a substrate on which a thin film has been formed by spin coating, slit coating, inkjet printing, etc., and drying the applied metal-containing photoresist composition to form a photoresist film.

[0037] The metal-containing photoresist composition may include an organometallic compound comprising at least one of an organic oxy group and an organic carbonyl oxy group.

[0038] As an example, the organometallic compound may contain at least one metal selected from Sn, Te, and Sb.

[0039] As a specific example, the organometallic compound may contain Sn.

[0040] The pattern forming method according to claim 3, wherein in one embodiment, the metal-containing photoresist composition may contain an organotin compound represented by the following chemical formula 1.

[0041] [ka]

[0042] In the above chemical formula 1, R 6 This is selected from substituted or unsubstituted C1-C20 alkyl groups, substituted or unsubstituted C3-C20 cycloalkyl groups, substituted or unsubstituted C2-C20 alkenyl groups, substituted or unsubstituted C2-C20 alkynyl groups, substituted or unsubstituted C6-C30 aryl groups, and substituted or unsubstituted C7-C30 arylalkyl groups. R 4 ~R 6 Each of these independently comprises a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C7-C30 arylalkyl group, an alkoxy, and an aryloxy (-OR) group. b Here, R b (which is a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof), a carboxyl group (-O(CO)R c , R c(where is hydrogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof), alkylamide or dialkylamide (-NR d R e Here, R d and R e Each of these is independently a hydrogen atom, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof), amidato (-NR f (COR g ), here R f and R g Each of these is independently hydrogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof), amidinato (-NR h C(NR i )R j Here, R h , R i , and R j Each of these is independently hydrogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof), alkylthio and arylthio (-SR k Here, R kis a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a combination thereof) or a thiocarboxyl group (-S(CO)R l where R l is hydrogen, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a combination thereof), and at least one of R 7 to R 9 is alkoxy and aryloxy (-OR b where R b is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a combination thereof), a carboxyl group (-O(CO)R c where R c is hydrogen, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a combination thereof), an alkylamide or a dialkylamide (-NR d R e where R d and R eis each independently hydrogen, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a combination thereof), amidato (-NR f (COR g ), where R f and R g are each independently hydrogen, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a combination thereof), amidinato (-NR g C(NR h )R i , where R h , R i , and R j are each independently hydrogen, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a combination thereof), alkylthio and arylthio (-SR k , where R k is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a combination thereof) and thiocarboxyl group (-S(CO)R l , R l(The group is selected from hydrogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof.)

[0043] For example, the R 7 ~R 9 At least one of them is an alkoxy and an aryloxy (-OR b Here, R b (wherein is a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof), and a carboxyl group (-O(CO)R c , R c (The carbon atom can be selected from hydrogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof.)

[0044] For example, the R 6 These are substituted or unsubstituted C1-C8 alkyl groups, substituted or unsubstituted C3-C8 cycloalkyl groups, substituted or unsubstituted C2-C8 aliphatic unsaturated organic groups containing one or more double or triple bonds, substituted or unsubstituted C6-C20 aryl groups, substituted or unsubstituted C4-C20 heteroaryl groups, carbonyl groups, ethoxy groups, propoxy groups, or combinations thereof. R bThese are substituted or unsubstituted C1-C8 alkyl groups, substituted or unsubstituted C3-C8 cycloalkyl groups, substituted or unsubstituted C2-C8 alkenyl groups, substituted or unsubstituted C2-C8 alkynyl groups, substituted or unsubstituted C6-C20 aryl groups, or combinations thereof. R c This may be hydrogen, a substituted or unsubstituted C1-C8 alkyl group, a substituted or unsubstituted C3-C8 cycloalkyl group, a substituted or unsubstituted C2-C8 alkenyl group, a substituted or unsubstituted C2-C8 alkynyl group, a substituted or unsubstituted C6-C20 aryl group, or a combination thereof.

[0045] In another embodiment, the metal-containing photoresist composition may contain an organotin compound represented by the following chemical formula 2 or chemical formula 3.

[0046] [ka] In the above chemical formula 2, R 10 These are hydrocarbyl groups with 1 to 31 carbon atoms, where 0 <z≦2であり、0<(z+x)≦4であり; [ka] In the above chemical formula 3, R 11 These are substituted or unsubstituted C1-C20 alkyl groups, substituted or unsubstituted C3-C20 cycloalkyl groups, substituted or unsubstituted C2-C20 aliphatic unsaturated organic groups containing one or more double or triple bonds, substituted or unsubstituted C6-C30 aryl groups, substituted or unsubstituted C4-C30 heteroaryl groups, carbonyl groups, ethylene oxide groups, propylene oxide groups, or combinations thereof. X is sulfur (S), selenium (Se), or tellurium (Te). Y is -OR m Or -OC(=O)R n And, The aforementioned R m These are substituted or unsubstituted C1-C20 alkyl groups, substituted or unsubstituted C3-C20 cycloalkyl groups, substituted or unsubstituted C2-C20 alkenyl groups, substituted or unsubstituted C2-C20 alkynyl groups, substituted or unsubstituted C6-C30 aryl groups, or combinations thereof. R n These are hydrogen, substituted or unsubstituted C1-C20 alkyl groups, substituted or unsubstituted C3-C20 cycloalkyl groups, substituted or unsubstituted C2-C20 alkenyl groups, substituted or unsubstituted C2-C20 alkynyl groups, substituted or unsubstituted C6-C30 aryl groups, or combinations thereof. The terms a, b, c, and d are each independent integers between 1 and 20.

[0047] Next, a first heat treatment step is performed in which the substrate on which the metal-containing photoresist film is formed is heated. The first heat treatment step can be performed at a temperature of approximately 80°C to approximately 120°C, during which the solvent evaporates and the metal-containing photoresist film can adhere more firmly to the substrate.

[0048] Then, the photoresist film is selectively exposed.

[0049] As an example, examples of light that can be used in the exposure process include not only short-wavelength light such as the activation irradiation diagram i-line (wavelength 365 nm), KrF excimer laser (wavelength 248 nm), and ArF excimer laser (wavelength 193 nm), but also high-energy wavelength light such as EUV (Extreme UltraViolet; wavelength 13.5 nm) and E-Beam (electron beam).

[0050] More specifically, the exposure light in one embodiment may be light having a wavelength range of 5 nm to 150 nm, or it may be light having a high energy wavelength such as EUV (Extreme UltraViolet; wavelength 13.5 nm) or E-Beam (electron beam).

[0051] During the process of forming the photoresist pattern, a negative-type pattern can be formed.

[0052] The exposed regions in the photoresist film develop different solubility from the unexposed regions of the photoresist film by forming polymers through crosslinking reactions such as condensation between organometallic compounds.

[0053] Next, a second heat treatment step is performed on the substrate. This second heat treatment step can be carried out at a temperature of approximately 90°C to approximately 200°C. By performing this second heat treatment step, the exposed area of ​​the photoresist film becomes less soluble in the developer solution.

[0054] Specifically, by dissolving the photoresist film corresponding to the unexposed region using the aforementioned photoresist developer and then removing it, the photoresist pattern corresponding to the negative tone image can be completed.

[0055] As mentioned above, photoresist patterns formed by exposure with light having wavelengths such as i-line (wavelength 365nm), KrF excimer laser (wavelength 248nm), and ArF excimer laser (wavelength 193nm), as well as high-energy light such as EUV (Extreme UltraViolet; wavelength 13.5nm) and E-Beam (electron beam), can have a width of 5nm to 100nm in thickness. For example, the photoresist patterns can be formed with thicknesses of 5nm to 90nm, 5nm to 80nm, 5nm to 70nm, 5nm to 60nm, 5nm to 50nm, 5nm to 40nm, 5nm to 30nm, and 5nm to 20nm.

[0056] On the other hand, the photoresist pattern may have a half-pitch of approximately 50 nm or less, for example 40 nm or less, for example 30 nm or less, for example 20 nm or less, for example 15 nm or less, and a pitch having a line width roughness of approximately 10 nm or less, approximately 5 nm or less, approximately 3 nm or less, or approximately 2 nm or less.

[0057] The following will explain in detail how to form the pattern, using diagrams as examples.

[0058] Figure 1 is a cross-sectional view showing the process sequence to illustrate the pattern formation method.

[0059] Referring to Figure 1(a), the exposed photoresist film is developed to form the photoresist pattern 130P.

[0060] In an exemplary embodiment, an exposed photoresist film can be developed to remove unexposed regions of the photoresist film, thereby forming a photoresist pattern 130P consisting of the exposed regions of the photoresist film. The photoresist pattern 130P may include a plurality of apertures OP.

[0061] In an exemplary embodiment, the photoresist film can be developed using a negative-tone development (NTD) process. In this case, a metal-containing photoresist developer composition according to one embodiment can be used as the developer composition.

[0062] Referring to Figure 1(b), the feature layer 110 is processed using the photoresist pattern 130P with the result of (a).

[0063] For example, various processes can be performed to process the feature layer 110, such as etching the feature layer 110 exposed through the aperture OP of the photoresist pattern 130P, implanting impurity ions into the feature layer 110, forming an additional film on the feature layer 110 through the aperture OP, and deforming a part of the feature layer 110 through the aperture OP. Figure 1(b) illustrates an example of a process for processing the feature layer 110, where the feature layer 110 exposed through the aperture OP is etched to form the feature pattern 110P. The feature pattern 110P is located on the substrate 100.

[0064] Referring to Figure 1(c), the photoresist pattern 130P remaining on the feature pattern 110P in the result of (b) is removed. Ashing and stripping processes can be used to remove the photoresist pattern 130P. [Examples]

[0065] The present invention will be described in more detail below through the examples relating to the production of the aforementioned metal-containing photoresist developer composition. However, the technical features of the present invention are not limited by the following examples.

[0066] Organometallic compounds (clusters containing 21 Sn molecules ((t-Bu)3Sn3(O2CH)5(OH)2O)) were dissolved in 3% Propylene glycol methyl ether acetate (PGMEA), and then filtered through a 0.1 μm PTFE (polytetrafluoroethylene) syringe filter to produce a semiconductor photoresist composition. This composition was then spin-coated onto an 8-inch wafer at 1,500 rpm for 30 seconds, followed by heat treatment at 160°C for 60 seconds to produce a coated wafer. Subsequently, an exposure energy of 7-25 mJ / cm² was applied. 2 KrF exposure and PEB processes were performed in stages within the specified range.

[0067] Subsequently, as shown in Table 1 below, a film with a pattern formed is manufactured by developing it through different exposure energy levels using a developer composition containing the solvent. The thickness of the dissolved film is measured, and the contrast curve showing the relative thickness after dissolution (thickness of the photoresist film developed after exposure at the second exposure energy / thickness of the photoresist film developed after exposure at the first exposure energy) is used to classify the film as soluble if the remaining film thickness is 20% or less, and insoluble if it exceeds 20%. The HSP Sphere is then calculated based on data input from solubility charts for at least five solvents. The solubility parameter simulation is performed using the methodology presented in the paper "Calculating hansen solubility parameters of polymers with genetic algorithms" G. Canete Vebber et al., J. Appl. Polym. Sci., 2014, by performing a data fit to maximize the solubility score and then performing a Hansen solubility parameter simulation to determine the solubility factor and solubility radius R of the photoresist. a , R b Find (x, a) <R a and (x, b) > R b We can find the range in which the relationship holds.

[0068] [Table 1]

[0069] S1: AcAc (Acetyl acetone) S2: PGMEA(Propylene glycol methyl ether acetate) / AcAc=90 / 10(wt% / wt%) S3: PGMEA(Propylene glycol methyl ether acetate) / AcAc=80 / 20(wt% / wt%) S4: PGMEA(Propylene glycol methyl ether acetate) / AcAc=70 / 30(wt% / wt%) S5: GBL (γ-butyrolactone) S6:GBL / AcAc=80 / 20(wt% / wt%) S7: PGMEA S8: AA (Acetic acid) S9: n-butyl acetate S10:MIBC(Methyl isobutyl carbinol) S11: PGMEA / AA = 98 / 2 (wt% / wt%) S12: PGMEA / AA = 60 / 40 (wt% / wt%) S13:2-Heptanone S14:2-butanol S15: Anisole (or methoxybenzene)

[0070] Evaluation: Sensitivity / Scum and Bridge Evaluation The aforementioned organometallic semiconductor photoresist composition was spin-coated onto an 8-inch wafer at 1,500 rpm for 30 seconds, and then heat-treated at 160°C for 60 seconds to produce a coated wafer.

[0071] Subsequently, a linear array of 50 circular pads with a diameter of 500 μm was projected onto a wafer coated with the photoresist composition using EUV light (Lawrence Berkeley National Laboratory Micro Exposure Tool, MET). The pad exposure time was adjusted to ensure that an increasing dose of EUV light was applied to each pad.

[0072] Subsequently, the resist and substrate were exposed on a hot plate at 160°C for 120 seconds and then fired. The fired film was then subjected to a development process at 1,500 rpm for 30 seconds using the developer compositions from Examples 1-6 and Comparative Examples 1-9, followed by curing at 240°C for 60 seconds.

[0073] As a result, a 1:1 LS pattern with a line width of 50 nm was formed.

[0074] Optimal exposure dose Eop(μC / cm²) for forming a target-size LS pattern 2 The optimal exposure dose Eop(μC / cm²) was determined. 2 When the irradiation dose is reduced while minimizing the space dimensions, the minimum exposure dose at which a pattern can be formed without defects such as scum or bridging is defined as E0, and this is shown in Table 2.

[0075] The resist linewidth for exposed dose (energy) changes was measured using a CD-SEM. The appropriate sensitivity E for each exposure amount was determined from the resist linewidth values ​​formed differently for each exposure dose. gel This was confirmed. Furthermore, the degree of scum and bridge formation was examined from the CD-SEM images, and the results are shown in Table 2.

[0076] [Table 2]

[0077] Referring to Table 2, E0 and E in Examples 1 to 6 gel It can be confirmed that the noise level is lower, sensitivity is improved, and there is no occurrence of scum or bridging.

[0078] Although specific embodiments of the present invention have been described and illustrated above, it is obvious to those ordinary skill in the art that the present invention is not limited to the described embodiments and can be modified and transformed in various ways without departing from the spirit and scope of the invention. Therefore, such modifications or variations should not be understood individually from the technical spirit or viewpoint of the present invention, and the modified embodiments should be considered to fall within the scope of the claims of the present invention. [Explanation of Symbols]

[0079] 100...Substrate, OP...Aperture, 110...Feature layer, 110P...Feature pattern, 130P...Photoresist pattern.

Claims

1. A developer composition applicable to metal-containing photoresists, The aforementioned metal-containing photoresist is administered at a rate of 9 to 12 mJ / cm². ２ The coordinate a is determined by the Hansen solubility parameters (δd, δp, δh) of the first photoresist exposed at the first exposure energy; The metal-containing photoresist is exposed at a rate of 5 to 10 mJ / cm² relative to the first exposure energy. ２ Coordinate b is identified by the Hansen solubility parameters (δd, δp, δh) of the second photoresist exposed with an increased second exposure energy; and For a coordinate x specified by the Hansen solubility parameters (δd, δp, δh) of the developer composition, The dissolvable radius R with coordinate a as its center value. ａ Calculate, The dissolvable radius R with coordinate b as its center value. ｂ Calculate, For the distance (x, a) between coordinate x and coordinate a, and the distance (x, b) between coordinate x and coordinate b, calculated by the following formula 1: (x, a) < R ａ and (x, b) > R ｂ A metal-containing photoresist developer composition that satisfies the following relationship: <Formula 1> (x、a) ２ =4(δd ｘ -δd ａ ) ２ +(δp ｘ -δp ａ ) ２ +(δh ｘ -δh ａ ) ２ (x、b) ２ =4(δd ｘ -δd ｂ ) ２ +(δp ｘ -δp ｂ ) ２ +(δh ｘ -δh ｂ ) ２ (The aforementioned Hansen solubility parameter (HSP), solubility radius R) ａ and solubility radius R ｂ (This was predicted using the Generate Hansen Parameters module of the COSMOquick22 version program.)

2. The developer composition includes ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol methyl ether, diethylene glycol ethyl ether, propylene glycol, propylene glycol methyl ether (PGME), propylene glycol methyl ether acetate (PGMEA), propylene glycol ethyl ether, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, propylene glycol butyl ether, propylene glycol butyl ether acetate, ethanol, propanol, isopropyl alcohol, 2-butanol, isobutyl alcohol 4-methyl-2-pentanol, hexanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, ethylene glycol, propylene glycol, heptanone, propylene carbonate, butylene carbonate, toluene, xylene, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-heptanone, acetylacetone, acetic acid, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate (methyl The metal-containing photoresist developer composition according to claim 1, comprising pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, gamma-butyrolactone, methyl-2-hydroxyisobutyrate, methoxybenzene, n-butyl acetate, 1-methoxy-2-propyl acetate, methoxyethoxypropionate, ethoxyethoxypropionate, or a mixture thereof.

3. A step of applying a metal-containing photoresist composition onto a substrate; A heat treatment step in which a metal-containing photoresist film is formed on the substrate by drying and heating; The step of exposing the metal-containing photoresist film; and The step of developing using a metal-containing photoresist developer composition according to claim 1 or claim 2. A pattern formation method including the following.

4. The pattern forming method according to claim 3, wherein the metal-containing photoresist composition comprises an organometallic compound containing at least one of an organic oxy group and an organic carbonyl oxy group.

5. The pattern-forming method according to claim 4, wherein the organometallic compound comprises at least one metal selected from Sn, Te, and Sb.

6. The pattern forming method according to claim 4, wherein the organometallic compound includes Sn.

7. The pattern forming method according to claim 3, wherein the metal-containing photoresist composition comprises an organotin compound represented by the following chemical formula 1. 【Chemistry 1】 In the above chemical formula 1, R ６ This is selected from substituted or unsubstituted C1-C20 alkyl groups, substituted or unsubstituted C3-C20 cycloalkyl groups, substituted or unsubstituted C2-C20 alkenyl groups, substituted or unsubstituted C2-C20 alkynyl groups, substituted or unsubstituted C6-C30 aryl groups, and substituted or unsubstituted C7-C30 arylalkyl groups. R ４ ~R ６ Each of these independently comprises a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C7-C30 arylalkyl group, an alkoxy and an aryloxy (-OR ｂ Here, R ｂ (These are substituted or unsubstituted C1-C20 alkyl groups, substituted or unsubstituted C3-C20 cycloalkyl groups, substituted or unsubstituted C2-C20 alkenyl groups, substituted or unsubstituted C2-C20 alkynyl groups, substituted or unsubstituted C6-C30 aryl groups, or combinations thereof), carboxyl groups (-O(CO)R ｃ , R ｃ (These are hydrogen, substituted or unsubstituted C1-C20 alkyl groups, substituted or unsubstituted C3-C20 cycloalkyl groups, substituted or unsubstituted C2-C20 alkenyl groups, substituted or unsubstituted C2-C20 alkynyl groups, substituted or unsubstituted C6-C30 aryl groups, or combinations thereof), alkylamides or dialkylamides (-NR ｄ R ｅ Here, R ｄ and R ｅ Each is independently a hydrogen atom, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof), amidato (-NR ｆ (COR ｇ ), here R ｆ and R ｇ Each is independently a hydrogen atom, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof), amidinato (-NR ｈ C (NR ｉ ) R ｊ Here, R ｈ , R ｉ , and R ｊ Each of these is independently hydrogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof), alkylthio and arylthio (-SR ｋ Here, R ｋ (which is a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof) or a thiocarboxyl group (-S(CO)R ｌ , R ｌ (These are hydrogen, substituted or unsubstituted C1-C20 alkyl groups, substituted or unsubstituted C3-C20 cycloalkyl groups, substituted or unsubstituted C2-C20 alkenyl groups, substituted or unsubstituted C2-C20 alkynyl groups, substituted or unsubstituted C6-C30 aryl groups, or combinations thereof.) R ７ ~R ９ At least one of them is an alkoxy and an aryloxy (-OR ｂ Here, R ｂ (These are substituted or unsubstituted C1-C20 alkyl groups, substituted or unsubstituted C3-C20 cycloalkyl groups, substituted or unsubstituted C2-C20 alkenyl groups, substituted or unsubstituted C2-C20 alkynyl groups, substituted or unsubstituted C6-C30 aryl groups, or combinations thereof), carboxyl groups (-O(CO)R ｃ , R ｃ (These are hydrogen, substituted or unsubstituted C1-C20 alkyl groups, substituted or unsubstituted C3-C20 cycloalkyl groups, substituted or unsubstituted C2-C20 alkenyl groups, substituted or unsubstituted C2-C20 alkynyl groups, substituted or unsubstituted C6-C30 aryl groups, or combinations thereof), alkylamides or dialkylamides (-NR ｄ R ｅ Here, R ｄ and R ｅ Each is independently a hydrogen atom, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof), amidato (-NR ｆ (COR ｇ ), here R ｆ and R ｇ Each is independently a hydrogen atom, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof), amidinato (-NR ｇ C (NR ｈ ) R ｉ Here, R ｈ , R ｉ , and R ｊ Each of these is independently hydrogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof), alkylthio and arylthio (-SR ｋ Here, R ｋ (which is a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof) and a thiocarboxyl group (-S(CO)R ｌ , R ｌ (The carbon atom is selected from hydrogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof.)

8. The aforementioned R ７ ~R ９ At least one of them is an alkoxy and an aryloxy (-OR ｂ Here, R ｂ (wherein is a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof), and a carboxyl group (-O(CO)R ｃ , R ｃ The pattern forming method according to claim 7, wherein is selected from hydrogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof.

9. The aforementioned R ６ These are substituted or unsubstituted C1-C8 alkyl groups, substituted or unsubstituted C3-C8 cycloalkyl groups, substituted or unsubstituted C2-C8 aliphatic unsaturated organic groups containing one or more double or triple bonds, substituted or unsubstituted C6-C20 aryl groups, substituted or unsubstituted C4-C20 heteroaryl groups, carbonyl groups, ethoxy groups, propoxy groups, or combinations thereof. R ｂ These are substituted or unsubstituted C1-C8 alkyl groups, substituted or unsubstituted C3-C8 cycloalkyl groups, substituted or unsubstituted C2-C8 alkenyl groups, substituted or unsubstituted C2-C8 alkynyl groups, substituted or unsubstituted C6-C20 aryl groups, or combinations thereof. R ｃ The pattern forming method according to claim 7, wherein is hydrogen, a substituted or unsubstituted C1-C8 alkyl group, a substituted or unsubstituted C3-C8 cycloalkyl group, a substituted or unsubstituted C2-C8 alkenyl group, a substituted or unsubstituted C2-C8 alkynyl group, a substituted or unsubstituted C6-C20 aryl group, or a combination thereof.

10. The pattern forming method according to claim 3, wherein the metal-containing photoresist composition comprises an organotin compound represented by the following chemical formula 2 or chemical formula 3: 【Chemistry 2】 In the above chemical formula 2, R １０ is a hydrocarbyl group having 1 to 31 carbon atoms, where 0 < z ≤ 2 and 0 < (z + x) ≤ 4; 【Transformation 3】 In the above chemical formula 3, R １１ These are substituted or unsubstituted C1-C20 alkyl groups, substituted or unsubstituted C3-C20 cycloalkyl groups, substituted or unsubstituted C2-C20 aliphatic unsaturated organic groups containing one or more double or triple bonds, substituted or unsubstituted C6-C30 aryl groups, substituted or unsubstituted C4-C30 heteroaryl groups, carbonyl groups, ethylene oxide groups, propylene oxide groups, or combinations thereof. X is sulfur (S), selenium (Se), or tellurium (Te), Y is -OR ｍ or -OC(=O)R ｎ wherein The aforementioned R ｍ These are substituted or unsubstituted C1-C20 alkyl groups, substituted or unsubstituted C3-C20 cycloalkyl groups, substituted or unsubstituted C2-C20 alkenyl groups, substituted or unsubstituted C2-C20 alkynyl groups, substituted or unsubstituted C6-C30 aryl groups, or combinations thereof. R ｎ These are hydrogen, substituted or unsubstituted C1-C20 alkyl groups, substituted or unsubstituted C3-C20 cycloalkyl groups, substituted or unsubstituted C2-C20 alkenyl groups, substituted or unsubstituted C2-C20 alkynyl groups, substituted or unsubstituted C6-C30 aryl groups, or combinations thereof. The terms a, b, c, and d are each independent integers between 1 and 20.

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