Positive pattern from metal organic resist

Abstract

The present invention and claimed subject matter relate to the use of metal organic resist (MOR) resists in positive processing in high resolution patterning using actinic radiation, in particular EUV radiation having a wavelength of 13.5 nm.

Description

TECHNICAL FIELD

[0001] The present invention and claimed subject matter relates to the use of metal organic resist (MOR) resists in positive tone processing in high resolution patterning using actinic radiation, especially EUV radiation at a wavelength of 13.5 nm.

[0002] PRIOR ART

[0003] Metal organic resists (MOR) have been found to be useful in EUV lithography as they exhibit a high absorption cross section for EUV radiation. So far, MORs have only been described for practical use in negative tone processing. While positive tone applications have been described a few times, the unexposed material lacks proper resistance to the developer under appropriate process conditions, resulting in unacceptable film loss.

[0004] U.S. Patent No. 9,310,684 describes a positive tone development using dry deposition of monobutyl tin oxo hydrate that reacts to form an oxohydroxy cluster. The process utilizes an aqueous developer, which can be basic or acidic, with a sharper pattern for the basic solution. A TMAH solution (2.5% as a standard developer solution in semiconductor technology) is indicated as preferred because there will be no metal contamination from the developer.

[0005] WO 22016123 describes the use of metal containing complexes and reactive co- reactants. Depending on the choice of co-reactant, the film can be developed as positive tone (as oxalyl derived groups) or negative tone. Notably, an aqueous basic solution is preferred for wet development, while an acid vapor is preferred for dry development. In addition, the disclosed system requires an additive in order to crosslink the cluster for resist.

[0006] A consistent problem with the above described positive tone development processes is the extremely short development time (on the order of seconds). If the polarity of the material is decreased, the development time can be increased. However, the only materials used include tin-oxo-hydroxy clusters; thus, they contain the hydroxyl group that leads to the undesirable short development time.

[0007] The use of the Sn6 cluster described herein provides the advantage of the absence of a hydroxyl group. This allows the polarity to be adjusted by the choice of carboxylic acid used in the synthesis. This allows the development time to be adjusted significantly and makes the development process less sensitive to variations. As described herein, adjustment from less polar acids to more polar acids allows longer development times to be achieved. In addition, TMAH shows the best results in development time. A positive tone resist based on MOR has been demonstrated by using an aqueous developer. It can also be shown that adjusting the MOR to a less polar structure improves the development process. Additionally, the use of an underlayer provides better pattern retention by taking into account the variation in polarity of the MOR. SUMMARY

[0008] In one embodiment, the present invention and the claimed subject matter relate to the use of metal-organic resists (MORs) of the following general formula:

[0009]

[0010] Wherein R is a C1-C6 alkyl group (hereinafter referred to as "(R-Sn)6O6(O2C-dithiane)6"), used for positive patterning in high-resolution patterning using photochemical radiation. As those skilled in the art will understand, the above-described MOR is a Sn6-oxygen drum cluster having the following general structure:

[0011] .

[0012] In one aspect of this implementation, the photochemical radiation is EUV radiation with a wavelength of 13.5 nm.

[0013] This overview section does not specifically describe the novel aspects of each embodiment and / or increment. Instead, this overview provides only a preliminary discussion of different embodiments and their novel points relative to conventional and known technologies. For more details and / or possible perspectives on the invention and claimed subject matter and its embodiments, the reader is directed to the detailed description section below and the corresponding drawings of the invention.

[0014] For clarity, the order in which the different steps described herein are discussed has been presented. Generally, the steps disclosed herein can be performed in any suitable order. Furthermore, although each different feature, technique, configuration, etc., disclosed herein may be discussed in different parts of the invention, it is intended that each concept can be performed independently or appropriately combined with each other. Therefore, the invention and the claimed subject matter can be embodied and viewed in many different ways. Attached Figure Description

[0015] The accompanying drawings are included to provide a further understanding of the subject matter of the invention and are incorporated in and constitute a part of this specification. The drawings illustrate embodiments of the subject matter of the invention and, together with the description, serve to explain the principles of the subject matter. In the drawings:

[0016] Figure 1 It shows ( n The developing structure of Bu-Sn)6O6(O2CCH3)6;

[0017] Figure 2 It shows ( n The developing structure of Bu-Sn)6O6(O2CH)6;

[0018] Figure 3 The developed (shown in the comparative example) nBu-Sn)6O6(O2CCH3)6 (dashed line) and ( n The dose curve of the Bu-Sn)6O6(O2CH)6 (solid line) sample;

[0019] Figure 4 It shows ( n The developing structure of Bu-Sn)6O6(O2C dithiane)6;

[0020] Figure 5 It shows ( n The developing structure of Bu-Sn)6O6(O2C dithiane)6;

[0021] Figure 6 The developed (shown) n Dose curves of the Bu-Sn)6O6(O2C dithiazide)6 cluster;

[0022] Figure 7 The target with a 44 nm pitch is shown. n EUV exposure of Bu-Sn)6O6(O2C dithiane)6 (without lower layer);

[0023] Figure 8 The image shows a target with a 60 nm pitch. n EUV exposure of Bu-Sn)6O6(O2C dithiane)6 (with lower layer);

[0024] Figure 9 The target with a 44 nm pitch is shown. n EUV exposure of Bu-Sn)6O6(O2C dithiane)6 (with lower layer);

[0025] Figure 10 This shows a target with a 50 nm pitch and five minutes of TMAH development. n EUV exposure of Bu-Sn)6O6(O2C dithiane)6 (with a lower layer); and

[0026] Figure 11 This shows a target with a 44 nm pitch and a two-minute TMAH development followed by an additional 15-second TMAH rinse. n EUV exposure of Bu-Sn)6O6(O2C dithiane)6 (with lower layer).

[0027] definition

[0028] Unless otherwise stated, the following terms used in this application shall have the following meanings.

[0029] In this application, the use of the singular includes the plural, and the words “a,” “an,” and “the” mean “at least one,” unless otherwise specified. Furthermore, the word “including” and other forms such as “including” and “included” are not restrictive. Additionally, terms such as “element” or “component” include elements or components comprising one unit and elements or components comprising more than one unit, unless otherwise specified. The conjunction “and” as used herein is intended to be inclusive, and the conjunction “or” is not intended to be exclusive, unless otherwise indicated. For example, the phrase “or, alternatively” is intended to be exclusive. The term “and / or” as used herein refers to any combination of the foregoing elements, including the use of a single element.

[0030] When used in connection with a measurable numerical variable, the term “about” or “approximately” refers to the indicated value of the variable and all values ​​of the variable within the experimental error range of that indicated value (e.g., within the 95% confidence limit of the mean) or a percentage range of that indicated value (e.g., ±10%, ±5%), whichever is greater.

[0031] "Photochemical radiation" should be understood to include all forms of radioactive energy capable of causing chemical changes in photoresist compositions, excluding changes caused by purely thermal effects. Examples of collimated radiation include, but are not limited to, photons, electron beams, or other particle beams, including but not limited to, those with wavelengths of 13.5 nm, 193 nm, 248 nm, or 365 nm.

[0032] The "C" used in this article x-y (where x and y are each integers) specifies the number of carbon atoms in the chain. For example, C 1-6 Alkyl refers to an alkyl chain having 1 to 6 carbon atoms (e.g., methyl, ethyl, propyl, butyl, pentyl, and hexyl). Unless otherwise specified, the chain may be linear or branched.

[0033] Unless otherwise specified, "alkyl" refers to a hydrocarbon group that can be straight-chain, branched (e.g., methyl, ethyl, propyl, isopropyl, tert-butyl, etc.), cyclic (e.g., cyclohexyl, cyclopropyl, cyclopentyl, etc.), or polycyclic (e.g., norbornyl, adamantyl, etc.). Suitable acyclic groups can be methyl, ethyl, n- or iso-propyl, n-, iso- or tert-butyl, straight-chain or branched pentyl, hexyl, heptyl, octyl, decyl, dodecyl, tetradecyl, and hexadecyl. Unless otherwise specified, alkyl refers to a group with 1 to 10 carbon atoms. Cyclic alkyl groups can be monocyclic or polycyclic. Suitable examples of monocyclic alkyl groups include substituted cyclopentyl, cyclohexyl, and cycloheptyl groups. Substituents can be any acyclic alkyl group described herein. Suitable bicyclic alkyl groups include substituted bicyclic [2.2.1]heptane, bicyclic [2.2.2]octane, bicyclic [3.2.1]octane, bicyclic [3.2.2]nonane, and bicyclic [3.3.2]decane, etc. Examples of tricyclic alkyl groups include tricyclic [5.4.0.0]. 2,9 Undecane, tricyclo[4.2.1.2] 7,9 Undecane, tricyclo[5.3.2.0] 4,9 Dodecane and tricyclic [5.2.1.0] 2,6 Decane. As mentioned herein, cyclic alkyl groups can have any acyclic alkyl group as a substituent. These alkyl groups may be substituted or unsubstituted.

[0034] "Haloalkyl" refers to a straight-chain, cyclic, or branched saturated alkyl group as defined above, wherein one or more hydrogen atoms have been replaced by a halogen (e.g., F, Cl, Br, and I). Thus, for example, fluoroalkyl (also called "fluoroalkyl") refers to a straight-chain, cyclic, or branched saturated alkyl group as defined above, wherein one or more hydrogen atoms have been replaced by fluorine (e.g., trifluoromethyl, perfluoroethyl, 2,2,2-trifluoroethyl, perfluoroisopropyl, perfluorocyclohexyl, etc.). Such haloalkyl groups (e.g., fluoroalkyl groups) can be unsubstituted or further substituted if they are not fully halogenated / polyhalogenated.

[0035] "Alkoxy" (also known as "alkyloxy") refers to an alkyl group (e.g., methoxy, ethoxy, propoxy, butoxy, 1,2-isopropoxy, cyclopentoxy, cyclohexyloxy, etc.) linked by an oxygen (-O-) group as defined above. These alkoxy groups may or may not be substituted.

[0036] "Alkyl carbonyl" refers to an alkyl group (e.g., methyl carbonyl, ethyl carbonyl, propyl carbonyl, butyl carbonyl, cyclopentyl carbonyl, etc.) linked by a carbonyl (-C(=O)-) group as defined above. These alkyl carbonyl groups may or may not be substituted.

[0037] "Halogen" or "halogen group" refers to halogens (e.g., F, Cl, Br, and I).

[0038] "Hydroxyl group" (also known as "hydroxyl group") refers to the -OH group.

[0039] Unless otherwise stated, the term "substituted" when referring to alkyl, alkoxy, fluoroalkyl, etc., means these groups that also contain one or more substituents, including but not limited to the following substituents: alkyl, substituted alkyl, unsubstituted aryl, substituted aryl, alkoxy, alkylaryl, haloalkyl, halogen, hydroxyl, amino, and aminoalkyl. Similarly, the term "unsubstituted" means these same groups that have no substituents other than hydrogen.

[0040] Aryl groups contain 6 to 24 carbon atoms and include phenyl, tolyl, xylyl, naphthyl, anthracene, biphenyl, diphenyl, triphenyl, etc. These aryl groups may be further substituted by any suitable substituents described herein, such as alkyl, alkoxy, acyl, or aryl groups. Similarly, suitable polyvalent aryl groups may be used in this invention as needed. Representative examples of divalent aryl groups (arylenes) include phenylene, xylene, naphthylene, biphenylene, etc. As used herein and unless otherwise specified, the term "aromatic" refers to a delocalized conjugated π system having 4 to 20 carbon atoms (aromatic C4-C). 20 Aromatic hydrocarbons are unsaturated cyclic hydrocarbons. Examples of aromatic hydrocarbons include, but are not limited to, benzene, toluene, xylene, mesitylene, ethylbenzene, cumene, naphthalene, methylnaphthalene, dimethylnaphthalene, ethylnaphthalene, acenaphthene, anthracene, phenanthrene, tetrabenzene, naphthene, benzene, fluoranthene, pyrene, β-benzene, triphenylene, and combinations thereof. Aromatic hydrocarbons may optionally be substituted, for example, with one or more alkyl groups, alkoxy groups, halogens, etc. For example, aromatic hydrocarbons may include anisole. Furthermore, aromatic hydrocarbons may include one or more heteroatoms. Examples of heteroatoms include, but are not limited to, nitrogen, oxygen, phosphorus, boron, and / or sulfur. Aromatic hydrocarbons having one or more heteroatoms include, but are not limited to, furan, benzofuran, thiophene, benzothiophene, oxazole, thiazole, and combinations thereof. Aromatic hydrocarbons may include monocyclic, bicyclic, tricyclic, and / or polycyclic (in some embodiments, at least monocyclic, only monocyclic and bicyclic, or only monocyclic) and may be fused rings.

[0041] The term "non-aromatic" refers to four or more carbon atoms bonded in at least one ring structure, wherein at least one of the four or more carbon atoms in the ring structure is a non-aromatic carbon atom.

[0042] Section headings used herein are for organizational purposes and are not to be construed as limiting the subject matter described. All references or portions thereof cited herein, including but not limited to patents, patent applications, articles, books, and textbooks, are incorporated herein by reference in their entirety for any purpose. Where incorporated references and similar materials define terms in a manner that contradicts the definition used in this application, this application shall have control.

[0043] All references, sources, articles, patents, and patent applications mentioned in this article are incorporated herein by reference in their entirety.

[0044] When the composition of the chemically scaled MOR described herein is expressed in weight percent (also known as wt%), it should be understood that in any case, the weight percent of all components (including non-essential components, such as impurities) will not exceed 100 wt%. In compositions consisting “substantially of” the components stated herein, these components may add up to 100 wt% of the composition, or may add up to less than 100 wt%. In cases where the components add up to less than 100 wt%, such compositions may contain small amounts of non-essential contaminants or impurities. For example, in one such embodiment, the formulation may contain 2 wt% or less of impurities. In another embodiment, the formulation may contain 1 wt% or less of impurities. In a further embodiment, the formulation may contain 0.05 wt% or less of impurities. In other such embodiments, the components may form at least 90 wt%, more preferably at least 95 wt%, more preferably at least 99 wt%, more preferably at least 99.5 wt%, most preferably at least 99.9 wt%, and may include other components that will not significantly affect the performance of the wet etchant. Otherwise, if no significant non-essential impurity components are present, it should be understood that the composition of all essential components substantially adds up to 100 wt%.

[0045] Detailed Explanation

[0046] It should be understood that the foregoing general description and the following detailed description are illustrative and explanatory, and do not limit the subject matter claimed in the claims. The objects, features, advantages, and concepts of the invention will be apparent to those skilled in the art from the description provided in the specification, and the invention will be readily practiced by those skilled in the art based on the description herein. For illustrative purposes, any “preferred embodiments” and / or examples, including preferred methods for carrying out the invention, are included and are not intended to limit the scope of the inventive subject matter disclosed herein.

[0047] It will also be apparent to those skilled in the art that, based on the aspects described in the specification, various modifications can be made to how the subject matter of the invention is practiced without departing from the spirit and scope of the inventive subject matter disclosed herein.

[0048] In one embodiment, the subject matter of the invention relates to the use of metal-organic resists (MOR) of the following general formula:

[0049]

[0050] Wherein R is a C1-C6 alkyl group (hereinafter referred to as "(R-Sn)6O6(O2C-dithiacyclohexane)6"), used for positive processing in high-resolution patterning using photochemical radiation. In one aspect of this embodiment, R is a methyl group. In one aspect of this embodiment, R is an ethyl group. In one aspect of this embodiment, R is a propyl group. In one aspect of this embodiment, R is a butyl group. In one aspect of this embodiment, R is an pentyl group. In one aspect of this embodiment, R is a hexyl group. In a preferred embodiment, R is a n-butyl group, and the cluster has the following formula

[0051]

[0052] (hereinafter referred to as "( n Bu-Sn)6O6(O2C-dithiacyclohexane)6”):

[0053] .

[0054] As shown above, the Sn-6 cluster comprises six (6) tin atoms with three oxygen bridges to other tin atoms, an organic group (in most cases an alkyl chain) directly bonded to tin, and two carboxylic acids bonded via one of the oxygen atoms of an acid. The acid can vary widely and can include hydrogen (as in formic acid), but may also include alkyl chains, phenyl groups, or organic groups with heteroatoms. These clusters are also known as drum-shaped clusters.

[0055] In another embodiment, the subject matter of the invention relates to the use of the aforementioned MOR for positive patterning in high-resolution patterning using photochemical radiation, wherein the method of using the MOR comprises, substantially comprises, or consists of the following steps: (i) spin-coating a composition comprising the aforementioned MOR (e.g., the composition disclosed above) and at least one spin-coating solvent onto a substrate; and (ii) exposing the spin-coated composition to photochemical radiation. Suitable substrates include silicon, aluminum, polymeric resins, silicon dioxide, doped silicon dioxide, silicon nitride, tantalum, copper, polycrystalline silicon, ceramics, aluminum / copper mixtures; gallium arsenide and other such Group III / V compounds. The resist may also be coated over an anti-reflective coating or other underlayer, including but not limited to underlayers specifically designed for EUV resist, or coated onto a hard mask, such as a hard mask for pattern transfer in a three-layer lamination process. In one aspect of this embodiment, the photochemical radiation is EUV radiation with a wavelength of 13.5 nm. In another aspect of this embodiment, the photochemical radiation is one of electron radiation and soft X-ray radiation.

[0056] In one aspect of this embodiment, at least one spin-coating solvent in step (i) comprises, substantially, or consists of one or more solvents suitable for spin coating. Examples of such solvents include, but are not limited to, glycol ether derivatives: such as ethyl cellosolve, methyl cellosolve, propylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, dipropylene glycol dimethyl ether, propylene glycol n-propyl ether, or diethylene glycol dimethyl ether; glycol ether ester derivatives: such as ethyl cellosolve acetate, methyl cellosolve acetate, or propylene glycol monomethyl ether acetate; carboxylic acid esters such as ethyl acetate, n-butyl acetate, and amyl acetate; carboxylic acid esters of dicarboxylic acids such as diethyl oxalate and diethyl malonate; dicarboxylic acid esters of glycols such as ethylene glycol diacetate and propylene glycol diacetate; hydroxycarboxylic acids. Esters such as methyl lactate, ethyl lactate, ethyl glycolate, and ethyl 3-hydroxypropionate; ketone esters such as methyl pyruvate or ethyl pyruvate; alkoxycarboxylic acid esters such as methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl 2-hydroxy-2-methylpropionate, or methyl ethoxypropionate; ketone derivatives such as methyl ethyl ketone, acetylacetone, cyclopentanone, cyclohexanone, or 2-heptanone; ketone ether derivatives such as diacetone alcohol methyl ether; ketone alcohol derivatives such as acetone alcohol or diacetone alcohol; lactones such as butyrolactone; amide derivatives such as dimethylacetamide or dimethylformamide, anisole, and mixtures thereof. In one embodiment, preferred solvents include propylene glycol monoalkyl ethers, propylene glycol alkyl (e.g., methyl) ether acetates, ethyl 3-ethoxypropionate, toluene, xylene, diethylene glycol dimethyl ether, amyl acetate, ethyl lactate, butyl acetate, 2-heptanone, ethylene glycol monoethyl ether acetate, and mixtures thereof. In another embodiment, preferred solvents include, but are not limited to, anisole, 4-methyl-2-pentanol, cyclohexanone, toluene, propylene glycol monomethyl ether, and 2-heptanone. In another aspect, the composition comprises more than one solvent.

[0057] On the other hand, the composition comprising the above-mentioned MOR and at least one spin-coatable solvent has a solvent content of about 49% to about 99% based on the total weight of the composition.

[0058] In another aspect of this embodiment, the method optionally further comprises, substantially consists of, or consists of (i-2) a post-application baking (“PAB”) heat treatment step of performing a spin-coated composition carried on a substrate prior to exposure (i.e., prior to step (ii)). The purpose of this step is to dry the spin-coated photoresist layer prior to exposure (i.e., to remove any residual solvent). This PAB step is also known as pre-baking or soft baking. PAB is typically performed on a hot plate or in an oven. For hot plate PAB, the preferred temperature is about 80°C to about 150°C, more preferably about 90°C to about 130°C, and most preferably about 90°C to about 120°C. For hot plate PAB, the preferred time is about 45 seconds to about 180 seconds, more preferably about 45 seconds to about 120 seconds, and most preferably about 60 seconds to about 120 seconds. Oven PAB may employ different times and temperatures depending on the type of oven and the contact method.

[0059] In another aspect of this embodiment, the method optionally further includes, substantially consists of, or comprises (iii) a post-exposure baking (“PEB”) step. In another aspect, the PEB is performed at a temperature above ambient temperature. In another aspect, the PEB is performed at a temperature between about 80°C and about 200°C. In another aspect, the PEB is performed at a temperature between about 90°C and about 170°C. In another aspect, the PEB is performed at a temperature between about 120°C and about 150°C. In another aspect, the PEB is performed at a temperature between about 150°C and about 180°C. In another aspect, the PEB is performed at a temperature of about 80°C. In another aspect, the PEB is performed at a temperature of about 85°C. In another aspect, the PEB is performed at a temperature of about 90°C. In another aspect, the PEB is performed at a temperature of about 100°C. In another aspect, the PEB is performed at a temperature of about 110°C. In another aspect, the PEB is performed at a temperature of about 120°C. In another aspect, the PEB is performed at a temperature of about 130°C. In another aspect, the PEB is performed at a temperature of about 140°C. On the other hand, PEB is performed at a temperature of approximately 150°C. On the other hand, PEB is performed at a temperature of approximately 160°C. On the other hand, PEB is performed at a temperature of approximately 170°C. On the other hand, PEB is performed at a temperature of approximately 180°C. On the other hand, PEB is performed at a temperature of approximately 190°C. On the other hand, PEB is performed at a temperature of approximately 200°C. On the other hand, PEB is performed for approximately 30 seconds to approximately 300 seconds. On the other hand, PEB is performed for approximately 50 seconds to approximately 180 seconds. On the other hand, PEB is performed for approximately 60 seconds to approximately 120 seconds.

[0060] In another aspect of this embodiment, the method further optionally includes, substantially consists of, or comprises (iv) the step of developing the substrate in a solvent. In this other aspect, the development of the substrate is performed for about 30 seconds to about 300 seconds. In this other aspect, the solvent developer is a polar solvent, such as ketone solvents, ester solvents, alcohol solvents, amide solvents, and ether solvents, and hydrocarbon solvents may be used. Examples of ketone solvents include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 2-heptanone, 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl ketone, cyclohexanone, methylcyclohexanone, acetone, methyl ethyl ketone, methyl isobutyl ketone, acetylacetone, acetone-based acetone, ionone, diacetone alcohol, acetylcarbene alcohol, acetophenyl, methylnaphthyl ketone, isophorone, and propylene carbonate. Examples of ester solvents include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl-3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate, and propyl lactate. Examples of alcohol solvents include alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, tert-butanol, isobutanol, n-hexanol, n-heptanol, n-octanol, and n-decanol; polyol solvents such as ethylene glycol, diethylene glycol, and triethylene glycol; and polyol ether solvents such as ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, triethylene glycol monoethyl ether, and methoxymethylbutanol. Examples of ether solvents include the aforementioned polyol ether solvents, dioxane, and tetrahydrofuran. Examples of amide solvents include N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, hexamethylphosphotriamide, and 1,3-dimethyl-2-imidazolinone. Examples of hydrocarbon solvents include aromatic hydrocarbon solvents, such as toluene and xylene, and aliphatic hydrocarbon solvents, such as pentane, hexane, heptane, octane, nonane, and decane, or petroleum fractions commonly referred to as white alcohol. Several of these solvents can be mixed, or the solvent can be used by mixing it with solvents other than those mentioned above, or by water.

[0061] In another aspect of this embodiment, the method optionally further comprises, substantially consists of, or consists of (v) a solvent rinsing step. Suitable solvents for rinsing include, but are not limited to, one or more hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents, and ether solvents. More preferably, after negative development, the step of washing the resist film with a rinsing solution containing at least one organic solvent selected from ketone solvents, ester solvents, alcohol solvents, and amide solvents is performed; more preferably, after development, the step of washing the resist film with a rinsing solution containing an alcohol solvent or an ester solvent is performed; even more preferably, after development, the step of washing the resist film with a rinsing solution containing a monohydric alcohol is performed. The polyols used in the rinsing step after negative development include straight-chain, branched, or cyclic monohydric alcohols, and specific examples of polyols that can be used preferably include 1-butanol, 2-butanol, 3-methyl-1-butanol, tert-butanol, 1-pentanol, 2-pentanol, 1-hexanol, 1-heptanol, 1-octanol, 2-hexanol, 2-heptanol, 2-octanol, 3-hexanol, 3-heptanol, 3-octanol, and 4-octanol. Alternatively, solvent rinsing may include more than one solvent.

[0062] In another aspect of the invention, the method further optionally comprises, substantially, or consists of step (vi) developing the substrate with an alkaline aqueous developer. In a further aspect, the development of the substrate lasts from about 30 seconds to about 300 seconds. In one embodiment, the developer is a buffered or unbuffered NaOH or KOH solution. In one embodiment, the aqueous developer is a metal ion-free (MIF) developer. Examples of such MIF developers include, but are not limited to, tetramethylammonium hydroxide (TMAH), tetra-n-butylammonium hydroxide (TBAH), tetraethylammonium hydroxide (TEAH), or choline hydroxide, at a concentration of 0.05 to 3N, preferably 0.1 to 3N, and most preferably 2.3 to 2.7N. A preferred developer is TMAH.

[0063] In one aspect of the invention, the developing step is followed by rinsing with an aqueous rinsing solution. This rinsing solution may include a surfactant that reduces its surface tension to below that of pure water. Such solutions are used to minimize pattern collapse due to capillary forces, which are theoretically predicted to be proportional to surface tension. They may also include other additives that reduce pattern collapse and help maintain the pattern shape of the resist structure during rinsing. Such solutions are described, for example, in M. Padmanaban et al., Proc. SPIE Vol. 8682, 868215 (2013), doi:10.1117 / 12.2013363; K. Yamamoto et al., Proc. SPIE, Vol. 10143, 101431X (2017), DOI:10.1117 / 12.2257393; and U.S. Patent No. 10,451,974.

[0064] In another aspect of the invention, the method optionally further comprises, substantially constitutes or consists of, a heat treatment step (i.e., hard baking) following step (vii) development and rinsing. This hard baking step can be carried out on a hot plate or in an oven, or optionally using microwave or infrared irradiation, including a rapid thermal annealing (RTA) system or a laser irradiation system. If hard baking is carried out on a hot plate, the preferred temperature is from about 110°C to about 300°C, more preferably from about 130°C to about 220°C. The preferred hard baking time on the hot plate is from about 30 seconds to about 300 seconds, more preferably from about 50 seconds to about 120 seconds. Hard baking time in an oven is typically longer than on a hot plate to compensate for lower heat transfer efficiency. Hard baking can be carried out under normal atmospheric conditions, under humidified conditions, under increased humidity conditions, in an oxygen-enriched atmosphere, in pure oxygen, or in an inert gas that excludes oxygen, including but not limited to nitrogen or argon. Detailed Implementation

[0065] Example

[0066] Reference will now be made to specific embodiments of the invention and experimental results supporting these embodiments. Examples are given below to more fully illustrate the disclosed subject matter and should not be construed as limiting the disclosed subject matter in any way.

[0067] It will be apparent to those skilled in the art that various modifications and variations can be made to the disclosed subject matter and the specific embodiments provided herein without departing from the spirit or scope of the disclosed subject matter. Therefore, the disclosed subject matter, including the description provided by the following embodiments, is intended to cover modifications and variations of the disclosed subject matter that fall within the scope of any claims and their equivalents.

[0068] Materials and methods:

[0069] The disclosed and claimed methods utilize commercially available materials (e.g., THF, PGME, cyclohexanone, toluene, formic acid, acetic acid, 1,3-dithiane-2-carboxylic acid (CAS 20461-89-6), CDCl3, C6D6). All cluster materials are prepared according to modified literature procedures. See Chandrasekhar et al., Inorg. Chem., 26, 1050 (1987).

[0070] Comparative example

[0071] Sn-6 formic acid group (i.e., ( n Bu-Sn)6O6(O2CH)6) and Sn-6 acetate cluster (i.e., ( n Photoresists for Bu-Sn)6O6(O2CCH3)6 were prepared at a concentration of 20 g / L in cyclohexanone (formic acid group); and at a concentration of 10 g / L in toluene (acetic acid group). These formulations were spin-coated onto Si wafers treated with oxygen plasma (400 W, 10 min). After soft baking at 100 °C for 2 min, a set of wafers was cleaved into smaller pieces, and the time required for complete removal of both coatings was determined using the TMAH-based developer AZ 726 MIF. For the formic acid group, this was 25 seconds; for the acetic acid group, it was 60 seconds.

[0072] Another set of coated wafers was exposed using an e-beam (30 kV) at dose levels ranging from 10 to 5000 μC / cm. 2 After exposure, the wafers were baked at 120°C for 2 minutes. Then, both wafers were developed using TMAH solution AZ 726 MIF for 13 seconds for formic acid clusters and 30 seconds for acetate clusters. The wafers were then rinsed with water and dried under nitrogen.

[0073] Figure 1 The pattern of Sn6 acetate clusters after development with TMAH is shown. Figure 2 The pattern of the Sn6 formic acid cluster after development with TMAH is shown. Figure 3 The developed Sn6 formic acid cluster is shown. n Bu-Sn)6O6(O2CH)6) and Sn6 acetate cluster ( n The dose curve of Bu-Sn)6O6(O2CCH3)6).

[0074] from Figures 1-3 As can be seen, well-defined patterns can be observed for both clusters. The surface of the acetate cluster is rougher than that of the formic acid cluster after TMAH development, but the thickness loss is less than that of the formic acid cluster. Figure 3The dose profiles show that the acetate clusters have better contrast. This was expected given the very short development time of the formic acid clusters. Due to the low contrast of the formic acid clusters, it exhibits a higher light velocity, but the film thickness loss is as high as 50%.

[0075] Example 1

[0076] 10 g / L of ( n A resist formulation of Bu-Sn)6O6(O2C-dithiane)6 in toluene was applied and dried for 120 seconds at 3500 rpm and 100 °C. One coating was exposed to TMAH (2.36 wt%) for 300 seconds and showed no loss of film thickness. Another coating was applied with an e-beam at an accelerating voltage of 30 kV at a temperature of 10 to 5000 μC / cm. 2 Exposure at the dose level. After exposure for 120 seconds at 120°C and baking, the coating is developed in TMAH for 60 seconds and then rinsed with water.

[0077] Figure 4 and Figure 5 The result shows the effect after 60 seconds of processing with TMAH ( n The imaging structure of Bu-Sn)6O6(O2C-dithiaane)6. Figure 6 The developed (shown) n Dosage curves of the Bu-Sn)6O6(O2C-dithiaane)6 cluster. Figure 6 The dose curves show that, compared to the formic acid and acetate groups in the comparative examples, ( n Bu-Sn)6O6(O2C-dithiaane)6 has better sensitivity and better contrast.

[0078] Following the above results, EUV exposure was performed at the Paul Scherrer Institute in Villigen, Switzerland. 10 g / L of ( n A 25 nm film was obtained by spin-coating Bu-Sn)6O6(O2C-dithiane)6 resist in toluene. PAB was used at 100 °C and PEB at 120 °C. A development time of 120–300 seconds was used after PEB. First, patterning was performed on bare silicon wafers with varying pitches from 100 nm to 44 nm, followed by development with 120 sTMAH (2.38 wt%). Figure 7 As shown, severe pattern collapse was observed. Using a lower layer (Merck lower layer AZExpO6010) significantly improved the results under the same formulation and process conditions. Figure 8 The image shows the effect of a lower AZExp O6010 layer with a pitch of 60nm. nEUV patterning of the Bu-Sn)6O6(O2C-dithiane)6 cluster. At 67 mJ / cm² 2 The defined pattern was observed during development with TMAH (2.38 wt%) for 120 seconds. Figure 9 The image shows the effect of a lower AZExp O6010 layer with a 44nm pitch. n EUV patterning of the Bu-Sn)6O6(O2C-dithiane)6 cluster. At 62 mJ / cm² 2 The defined pattern was observed under 120sTMAH (2.38wt%) development.

[0079] Unexposed ( n The Bu-Sn)6O6(O2C-dithiane)6 cluster exhibits resistance to TMAH (2.38 wt%) greater than 300 seconds. The same formulation, i.e., 10 g / L in toluene (… n The resist Bu-Sn)6O6(O2C-dithiane)6 is used on AZExp O6010, but with a longer development time of 300 seconds. Figure 10 The image shows the effect of a lower AZExp O6010 layer with a 50nm pitch. n EUV patterning of the Bu-Sn)6O6(O2C-dithiane)6 cluster at 49 mJ / cm 2 The defined pattern is displayed below. Figure 11 The same (shown) n The formula is Bu-Sn)6O6(O2C-dithiane)6, but includes a further 20-second TMAH (2.38%) rinse after the initial 120-second development. Figure 11 The image shows the effect of a lower AZExp O6010 layer with a 44nm pitch. n EUV patterning of the Bu-Sn)6O6(O2C-dithiane)6 cluster. At 53 mJ / cm² 2 The defined pattern observed showed reduced scum compared to no rinsing or an extended 300-second development time.

[0080] Although the disclosed and claimed subject matter has been described and illustrated with a degree of specificity, it should be understood that the invention has been made by way of example only, and those skilled in the art can make many changes to the order of conditions and steps without departing from the spirit and scope of the disclosed and claimed subject matter.

Claims

1. A method for positive type processing, comprising the following steps: (i) Spin-coating a composition comprising the following components onto a substrate: (a) A metal-organic resist (MOR) having the following formula: Where R is a C1-C6 alkyl group; and (b) at least one spin-coatable solvent; and (ii) Expose the spin-coated composition to photochemical radiation.

2. The method according to claim 1, wherein R is methyl.

3. The method according to claim 1, wherein R is ethyl.

4. The method according to claim 1, wherein R is propyl.

5. The method according to claim 1, wherein R is butyl.

6. The method according to claim 1, wherein R is pentyl.

7. The method of claim 1, wherein R is hexyl.

8. The method of claim 1, wherein the substrate of step (i) comprises one or more of silicon, aluminum, polymeric resin, silicon dioxide, doped silicon dioxide, silicon nitride, tantalum, copper, polycrystalline silicon, ceramic, aluminum / copper mixture, gallium arsenide, and other such group III / V compounds.

9. The method of claim 1, wherein the composition of step (i) is coated on one or more of an anti-reflective coating, a sublayer, and a hard mask.

10. The method according to claim 1, wherein at least one spin-coating solvent in step (i) comprises at least one of the following: glycol ether derivatives, glycol ether ester derivatives, carboxylic acid esters, carboxylic acid esters of dicarboxylic acids, dicarboxylic acid esters of glycol hydroxycarboxylic acids, ketone esters, alkoxycarboxylic acid esters, ketone derivatives, ketone ether derivatives, ketone alcohol derivatives, lactones, amide derivatives, anisole, and mixtures thereof.

11. The method according to claim 1, wherein at least one spin-coatable solvent in step (i) comprises at least one of the following: propylene glycol monoalkyl ether, propylene glycol alkyl (e.g., methyl) ether acetate, ethyl-3-ethoxypropionate, toluene, xylene, diethylene glycol dimethyl ether, amyl acetate, ethyl lactate, butyl acetate, 2-heptanone, ethylene glycol monoethyl ether acetate, and mixtures thereof.

12. The method according to claim 1, wherein at least one spin-coatable solvent in step (i) comprises at least one of the following: anisole, 4-methyl-2-pentanol, cyclohexanone, toluene, propylene glycol monomethyl ether, and 2-heptanone.

13. The method of claim 1, wherein at least one spin-coatable solvent in step (i) comprises more than one solvent.

14. The method according to claim 1, wherein the organometallic resist and at least one solvent in step (i) comprise about 49% to about 99% by weight of the composition.

15. The method of claim 1, wherein the photochemical radiation is EUV radiation with a wavelength of 13.5 nm.

16. The method of claim 1, wherein the photochemical radiation is one of electron radiation and soft X-ray radiation.

17. The method according to claim 1, further comprising step (i-2) of performing a post-coating baking ("PAB") heat treatment on the substrate carrying the spin-coated composition prior to step (ii).

18. The method of claim 1, further comprising (iii) a step of performing a post-exposure baking ("PEB") heat treatment on the substrate carrying the spin-coated composition after step (ii).

19. The method of claim 18, wherein the PEB occurs at a temperature above ambient temperature.

20. The method of claim 18, wherein the PEB occurs at a temperature between about 80°C and about 200°C.

21. The method of claim 18, wherein the PEB occurs at a temperature between about 90°C and about 170°C.

22. The method of claim 18, wherein the PEB occurs at a temperature between about 120°C and about 150°C.

23. The method of claim 18, wherein the PEB occurs at a temperature between about 150°C and about 180°C.

24. The method of claim 18, wherein PEB occurs at a temperature of about 80°C.

25. The method of claim 18, wherein PEB occurs at a temperature of about 85°C.

26. The method of claim 18, wherein PEB occurs at a temperature of about 90°C.

27. The method of claim 18, wherein PEB occurs at a temperature of about 100°C.

28. The method of claim 18, wherein PEB occurs at a temperature of about 110°C.

29. The method of claim 18, wherein PEB occurs at a temperature of about 120°C.

30. The method of claim 18, wherein PEB occurs at a temperature of about 130°C.

31. The method of claim 18, wherein PEB occurs at a temperature of about 140°C.

32. The method of claim 18, wherein PEB occurs at a temperature of about 150°C.

33. The method of claim 18, wherein PEB occurs at a temperature of about 160°C.

34. The method of claim 18, wherein PEB occurs at a temperature of about 170°C.

35. The method of claim 18, wherein the PEB lasts for about 30 seconds to about 300 seconds.

36. The method of claim 18, wherein the PEB lasts for about 50 seconds to about 180 seconds.

37. The method of claim 18, wherein the PEB lasts for about 60 seconds to about 120 seconds.

38. The method of claim 1, further comprising the step of developing the substrate in a solvent (iv).

39. The method of claim 38, wherein the substrate is developed in a solvent developer for about 30 seconds to about 300 seconds.

40. The method of claim 38, wherein the solvent developer comprises one or more polar solvents.

41. The method of claim 38, wherein the solvent developer comprises one or more of ketone solvents, ester solvents, alcohol solvents, amide solvents, ether solvents, and hydrocarbon solvents, or combinations thereof.

42. The method of claim 38, wherein the solvent developer comprises one or more of acetone, 2-heptanone, 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl ketone, cyclohexanone, methylcyclohexanone, phenylacetone, methyl ethyl ketone, methyl isobutyl ketone, acetylacetone, acetone-based acetone, ionone, diacetone alcohol, acetylcarbene alcohol, acetophenyl, methylnaphthyl ketone, isophorone, and propylene carbonate, and combinations thereof.

43. The method according to claim 38, wherein the solvent developer comprises one or more of methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl-3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate, and propyl lactate, and combinations thereof.

44. The method according to claim 38, wherein the solvent developer comprises one or more of methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, tert-butanol, isobutanol, n-hexanol, n-heptanol, n-octanol, decanol, ethylene glycol, diethylene glycol, triethylene glycol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, triethylene glycol monoethyl ether, and methoxymethylbutanol, and combinations thereof.

45. The method of claim 38, wherein the solvent developer comprises one or more of dioxane, tetrahydrofuran, and combinations thereof.

46. ​​The method of claim 38, wherein the solvent developer comprises one or more of N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, hexamethylphosphotriamide, and 1,3-dimethyl-2-imidazolinone, and combinations thereof.

47. The method of claim 38, wherein the solvent developer comprises one or more of toluene, xylene, pentane, hexane, heptane, octane, nonane, decane, and white alcohol, or combinations thereof.

48. The method of claim 1, further comprising a solvent rinsing step (v).

49. The method of claim 48, wherein the solvent in step (v) solvent rinsing comprises one or more of hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents, ether solvents, and combinations thereof.

50. The method of claim 48, wherein the solvent in step (v) solvent rinsing comprises one or more of 1-butanol, 2-butanol, 3-methyl-1-butanol, tert-butanol, 1-pentanol, 2-pentanol, 1-hexanol, 1-heptanol, 1-octanol, 2-hexanol, 2-heptanol, 2-octanol, 3-hexanol, 3-heptanal, 3-octanol, and 4-octanol, or combinations thereof.

51. The method of claim 1, further comprising the step (vi) of developing the substrate in an aqueous alkaline developer.

52. The method of claim 51, wherein the aqueous alkaline developer in step (vi) comprises one or more alkaline developers.

53. The method according to claim 51, wherein the aqueous alkaline developer in step (vi) comprises one or more of NaOH or KOH.

54. The method of claim 51, wherein the aqueous alkaline developer in step (vi) comprises one or more metal ion free (MIF) developers.

55. The method according to claim 51, wherein the aqueous alkaline developer in step (vi) comprises one or more of tetramethylammonium hydroxide (TMAH), tetra-n-butylammonium hydroxide, and choline hydroxide.

56. The method of claim 51, wherein the aqueous alkaline developer in step (vi) comprises tetramethylammonium hydroxide (TMAH).

57. The method according to claim 1, further comprising step (vii) of performing a heat treatment step after step (vi).

58. The method of claim 57, wherein the heat treatment is performed at a temperature of about 110°C to about 300°C.

59. The method of claim 57, wherein the heat treatment is performed at a temperature of about 130°C to about 220°C.

60. The method of claim 57, wherein the heat treatment is performed for about 30 seconds to about 300 seconds.

61. The method of claim 57, wherein the heat treatment is performed for about 50 seconds to about 120 seconds.

62. The method of claim 57, wherein the heat treatment is carried out under one or more of the following conditions: under atmospheric conditions, under conditions of humidity removal, under conditions of increased humidity, in an oxygen-enriched atmosphere, in pure oxygen, or in an inert gas in which oxygen is removed.

63. The following metal-organic resist (MOR) is used for positive processing in high-resolution patterning using photochemical radiation. Where R is a C1-C6 alkyl group.

64. The use according to claim 63, wherein R is a methyl group.

65. The use according to claim 63, wherein R is an ethyl group.

66. The use according to claim 63, wherein R is a propyl group.

67. The use according to claim 63, wherein R is a butyl group.

68. The use according to claim 63, wherein R is an pentyl group.

69. The use according to claim 63, wherein R is a hexyl group.

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