Silanol-containing organic-inorganic hybrid coatings for high resolution patterning

Abstract

To provide novel hydrogen silsesquioxane resin coating compositions.SOLUTION: A hydrogen silsesquioxane resin coating composition comprises in a liquid phase a resin exhibiting silanol (Si-OH) and silicon-hydrogen (Si-H) and optionally silicon-carbon bonds in a silicon-oxygen network, or silicon-hydrogen (Si-H) and optionally silicon-carbon bonds in a silicon-oxygen-metal network, a peak height ratio of Si-H to Si-OH being about 2:1 to 100:1.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a method for producing a coating composition for a substrate using a polyhydridosilsesquioxane resin coating composition. It relates to a radiation-based method for performing the patterning process.

[0002] Furthermore, the present invention provides very high resolution by applying masked radiation. A polyhydridosilsesquioxane resin coating that can be patterned with and deposited on coated materials and coatings formed from precursor solutions before and after patterning. The present invention relates to a hydrolysis precursor solution capable of [Background technology]

[0003] The miniaturization of complex circuits in microelectronic devices has traditionally been achieved through the creation of prescribable features. is limited by the wavelength of light used in the photolithography process. This has been achieved through advances in lithography processes that have been used for many years. Through this, 436nm (g-line), 405nm (h-line), 365nm (i-line), 248nm (KrF excimer 193 nm (ArF excimer) and finally 193 nm (ArF excimer) (Okoroanyanwu 2015, Gangnaik et al. .2017, De Simone et al.2014) have shifted to the defined wavelengths.

[0004] The resist material used at wavelengths of 248 nm and 193 nm is a chemically amplified resist (CAR). Their composition and microstructure are evolving to meet the needs of printing finer features on substrates. Continuing this trend, extreme ultraviolet (EUV) wavelengths of λ = 13.5 nm (92 eV) have It is a leading candidate for next-generation lithography (De Simone et al., 2017).

[0005] During the past decade, there have been significant advances in the development of Extreme Ultraviolet Lithography (EUVL) for the mass production of integrated circuits. Electron beam lithography (EBL), soft lithography, nanoimprint lithography (NIL), photon beam lithography (PBL), or scanning probe lithography There are various nanolithography techniques, including nanolithography, which can be used to print on two-dimensional surfaces. It was proposed to extend the feature reduction.

[0006] The success of EUVL requires new photoresist materials that face several advantages and disadvantages. Functional photoresists have RLS properties as described by Higgins et al. i.e., resolution (R), line edge roughness (LER), and sensitivity (S). be.

[0007] There are many different material approaches that have been developed for patterning using EUVL. At a general level, these are divided into three different classes of resists: organic, silicon-based, and metal-containing. They are classified into the following categories.

[0008] Organic resists, often referred to as non-CAR resists, can exhibit sufficient LER, but This is highly disadvantageous since high doses are required due to poor EUV absorption properties. In order to improve the photon transfer function, CAR materials were adopted. It suffers from poor LER resulting from the statistical effects of bit noise and photoacid generator distribution.

[0009] To address the challenges of both organic resists, the radiation-sensitive resist materials The formulation was prepared using the components: The most common element is a metal. Thus, metals are added to other resist materials to improve their sensitivity. Metal-containing resists that add metals, or molecular resists, metal oxide nanoparticles, and organometallic precursors. There is growing interest in metal-containing resists, either as precursors or as metal-organic frameworks. There are.

[0010] Such resists exhibit high sensitivity and high resolution and are considered to be important candidates for future EUVL resists. However, their main drawback is that the metal disrupts the function of the transistor. It is strongly disfavored in integrated circuit manufacturing due to the possibility of In addition, De Simone et al. and Watanabe reported that the metal-containing resin Metal species in the sample interact with atomic H or radical H*, severely affecting the optical lifetime. It has been noted that metal hydrides (MxHy) are formed. Furthermore, the high LER is due to the formation of metal-based and This is a problem for both CVD and chemically amplified resists (De Simone et al., 2017).

[0011] Another drawback of CAR is its low etching resistance and pattern instability (G Rigorescu and Hagen 2009). Therefore, CAR is a novel method for pattern transfer to a substrate. It requires both a silicon-rich intermediate layer and a carbon-rich underlayer. The inorganic resin used as the substrate is directly patterned by EUVL, so lithography is not required. This has the advantage that the system stack is simplified.

[0012] Hydrogen silsesquioxane (HSQ) is a widely used negative tone e-beam and EUVL Resist material. Due to the possibility of high density patterns, i.e. pitch structures of 10 nm or less Intensive research was carried out to find the optimum process. However, it was very low They suffer from poor sensitivity, require concentrated developers, and (Yang et al., 200 9), it is relatively unstable during processing which limits its industrial application. It is known that... Summary of the Invention

[0013] Developer temperature, developer concentration, developer composition, etc. to facilitate the development of processes suitable for EUVL. Despite the advances in the prior art, it is difficult to obtain RLS characteristics without excessive metal contamination. Functional photoresists that provide this functionality remain in demand.

[0014] An object of the present invention is to provide a novel hydrogen silsesquioxane resin coating composition. And so.

[0015] Another object of the present invention is to provide a method for producing the novel hydrogen silsesquioxane resin. And so.

[0016] The third object of the present invention is to provide a method for producing a polyhydridosilsesquioxane-coated substrate from which light can be emitted. The object of the present invention is to provide a method for patterning with

[0017] Further objects of the present invention include radiation sensitive coatings suitable for patterning by irradiation with light. The object of the present invention is to provide a coating substrate.

[0018] Conventional HSQ resins do not contain silanol groups. Surprisingly, in the present invention, HSQ resins The presence of silanol moieties in the polymer significantly increases the patterning ability of the coating compared to HSQ resins. As a result, it was found that the silanol-containing polyhydridosilsesquioxane of this type Sun has demonstrated a significant advance in EUV lithography compared to what has been described in the literature to date. It shows higher sensitivity.

[0019] The silanol groups of the resin present in the film are converted from SiH to intermediate reactive ketones generated by EUV. It appears that it reacts with isotope species, but this is only one possible explanation.

[0020] In addition, the sensitivity of polyhydridosilsesquioxane resins can be improved by adding functional groups. It was found that the addition of a silicon-containing precursor containing a functional group to the aqueous developer further enhanced the It also improves solubility.

[0021] Additionally, in some embodiments, a metal oxide compound may be included as part of the hydrolysis mixture. They can be used together or added separately as additives, or the nanoparticles can be used to improve the sensitivity of the resin. It has further been found that

[0022] Thus, the present invention provides a method for the production of silicon-oxygen-based nanotubes that are more efficient than Si-H or Si-R in silicon-oxygen networks. A silanol or silicon-carbon bond and a silicon-carbon bond are preferably present in the organic solvent. The present invention provides a solution of hydrogen silsesquioxane resin containing silicon-oxygen-metal with silicon-hydrogen. do.

[0023] The metal and silanol containing polyhydridosilsesquioxane resin solution of this kind is Trifunctional silanes are reacted with other silicon- or metal-containing precursors via hydrolysis / condensation to give polyhyridinium. by obtaining metal and silanol containing dodecylsilsesquioxanes. It is possible.

[0024] These solutions are then cast onto semiconductor substrates to form patterns thereon. These can be used to prepare hybrid organic-inorganic coatings.

[0025] The present invention also relates to a method for producing a silicon-oxygen or silicon-carbon bond and a silicon-hydrogen and / or The radiation-sensitive coating contains a silicon-oxygen-metal network with silanol bonds. The present invention provides a coated substrate comprising a coating material.

[0026] The present invention further provides a method for the production of polyhydridosilsesquioxane coatings by irradiation with light of specific wavelengths. A method for patterning metal and silanol containing substrates is provided, The method includes irradiating the coated substrate along a selected pattern to deposit a layer of the irradiated coating. forming an irradiated structure by arranging the area of ​​the coating and the area of ​​the unirradiated coating; The structure is selectively developed to remove a significant portion of the unexposed coating, forming a pattern. The method includes forming a substrate having a surface roughness of 100 nm.

[0027] Further, the present invention relates to a polyhydric silsesquioxane coated with radiation of a specific wavelength. A method for patterning metal and silanol containing quioxanes is provided, in which The length is less than 13.5 nm.

[0028] Furthermore, the present invention also provides a method for producing a substrate having a surface and a selected area along the surface, comprising: a first coating that is absent in other areas along the surface. Generally, the first coating is a silicon-oxygen or silicon-carbon bond. and silicon-oxygen-metal networks with silicon-hydrogen and / or silanol bonds. Alternatively, the first coating comprises a soluble compound that is soluble in at least some organic liquids. or the first coating is soluble in aqueous base.

[0029] More specifically, the invention is characterized by what is stated in the characterizing portions of the independent claims.

[0030] The present invention provides significant advantages.

[0031] Thus, the solutions of the present invention can be used to cast films onto semiconductor substrates and subsequently A pattern can be formed through the steps of baking, irradiating, and developing. To enable control of resin microstructure in an industrially feasible manner, and to overcome the shortcomings of the prior art For example, the silanol groups in metal- and silanol-containing polyhydridosilsesquioxane resins The fluorine content can be adjusted to obtain a highly sensitive coating for application in EUVL. Highly desirable for.

[0032] In addition, silicon-oxygen or silicon-carbon bonds and silicon-hydrogen and / or silicon The solubility of the coating containing silicon-oxygen-metal networks with lanol bonds is Modifying the coating by copolymerization of precursors that limit or enhance solubility in the developer It is possible.

[0033] The invention described herein addresses key RLS issues and further provides a method for fabricating a lithographic stack. It provides high oxygen plasma etch resistance allowing for simplification.

[0034] In addition, silicon-oxygen or silicon-carbon bonds and silicon-hydrogen and / or silano Use of coatings containing silicon oxygen-silicon oxygen-metal networks with metal bonds - Patents.com The present invention provides a method for forming a pattern by manipulating the dissolution characteristics of the irradiated coating in a developer. For development, it is possible to use the industry standard 2.38 wt % TMAH solution.

[0035] In an important aspect, the present invention provides a siloxane that can be patterned by irradiation. to deliver.

[0036] Further features and advantages of the present technology will become apparent from the following detailed discussion of the embodiments. . [Brief description of the drawings]

[0037] [Figure 1] FIG. 1 shows, in a side view, a schematic representation of the assembly of a three-layer lithographic stack. [Diagram 2] FIG. 2 shows a schematic side view of the assembly of a four-layer lithographic stack. [Diagram 3] FIG. 3 shows a schematic diagram in side view of patterning with metal and hydroxyl-containing polyhydridosilsesquioxane resin according to one embodiment. [Figure 4] FIG. 4 shows the EUV crosslinking mechanism of silanol-containing polyhydridosilsesquioxane. [Diagram 5] FIG. 5 is an SEM image showing 22 nm half pitch patterned lines with LER=1.5 nm obtained by EUVL using the material of Example 1 at an applied EUV dose of 65.4 mJ / cm 2 . [Figure 6] Figure 6a is an SEM image of 50 nm HP lines using 2% polymer prepared in Comparative Example 1 at a dose of 5000 μC / cm2. Figure 6b is an SEM image of 50 nm HP lines using 2% polymer prepared in Example 1 at a dose of 450 μC / cm2. [Figure 7]FIG. 7 shows the FTIR spectra of films prepared from the polymers in Examples 1, 3, and 5, and Comparative Examples 1 and 2, illustrating the difference in silanol content for the different syntheses. [Figure 8] Figure 8 includes three SEM images showing e-beam results for a) Example 1, b) Example 7, and c) Example 10 after irradiation. As can be seen from Figure 8, Examples 7 and 10 required 40% less dose than Example 1 to obtain similar patterns with improved LER. [Figure 9] FIG. 9 contains three SEM images showing e-beam results for a) Example 1, b) Example 14, and c) Example 17; as is evident from FIG. 9, the dose required to obtain the pattern was reduced by 17% in b) and 33% in c). [Figure 10] FIG. 10 contains three SEM images showing e-beam results for a) Example 1, b) Example 20, and c) Example 21, showing their performance at the same dose. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0038] An embodiment of the present invention involves hydrolysis of trifunctional silanes with suitable other silicon- or metal-containing precursors. Decomposition / condensation reactions to give metal- and silanol-containing polyhydridosilsesquioxanes The present invention relates to a method for producing a metal- and silanol-containing polyhydridosilsesquioxane resin solution. do.

[0039] The materials of the present invention can be characterized as "silanol-containing organic-inorganic hybrid materials." Such materials can be organic as well as inorganic compounds, as described below. Additionally, the materials of the present invention contain silanol groups, i.e., residues derived from the typical Specifically, the main chain is provided with groups exhibiting Si-O-H bonding, particularly along the main siloxane chain. Contains.

[0040] The silicon content of the resin or coating is typically at least 30% by weight, especially at least 35% by weight. And so on. Typically, the maximum value for silicon is about 52.9% by weight.

[0041] Generally, there is about one silsesquioxane per repeat unit of the polyhydrido-silsesquioxane resin backbone. In one embodiment, each unit of the polyhydridosilsesquioxane resin backbone is On average, there are about 0.8 to 1.2 silanol groups per unit area.

[0042] Thus, in one embodiment, silanol (Si—OH) and silicon-hydrogen (Si—H) The resin shown in FIG. 1 may have silicon-carbon bonds in a silicon-oxygen network, or silicon-carbon bonds in a silicon-oxygen network, as appropriate. Silicon-hydrogen (Si-H), optionally silicon-carbon in a silicon-oxygen-metal network Hydrogen silsesquioxane resin coating compositions are provided that contain bonds in the liquid phase, such as Si-H and S The peak height ratios of i-OH are about 2:1 to 100:1.

[0043] In one embodiment, a hydrogen silsesquioxane resin coating composition is provided, which comprises , about 0.001M to about 1M compared to Si-H or Si-R in the silicon-oxygen network. Silanol, or silicon-oxygen-metal having silicon-carbon and silicon-hydrogen bonds. It is a liquid phase.

[0044] The term "latent" when used in reference to an ingredient that is optionally present in the composition means: refers to a property that is activated during processing of the composition or resin, e.g., by light, and thus A "latent" catalyst is, for example, a catalyst that is activated when the resin or composition is exposed to light, particularly when the resin or composition is exposed to light. Similarly, the latent acids and bases in the composition become activated when exposed to light. It can be sexualized.

[0045] According to one embodiment, the present technique is suitable for forming a radiation curable siloxane layer on a substrate. The composition comprises a siloxane polymer containing a SiO moiety and a siloxane copolymer having a siloxane moiety. A plurality of reactive sites distributed along the first SiH moiety, the second SiOH moiety, and the intermediate aromatic and a fourth portion containing a metal-oxygen bond, the polymer comprising The composition preferably comprises an acid and / or further comprises a base catalyst and a solvent.

[0046] According to a preferred embodiment, the present technology provides a method for preparing a coating formulation that can be cast onto a substrate. For compositions suitable for manufacturing, the coating on the substrate is patterned by irradiation that can be patterned. The coating may be formed of a compound of formula (I): [ka] It is expressed as In formula (I), A, B, C, and D each independently represent an integer of 1 to 1000; Z represents a functional group; M represents a metal atom; R stands for child 1 ~R 8 each independently represents a hydrocarbyl radical; a, b, m, o, y, z, p, q, and x each independently represent an integer of 0 to 3.

[0047] The composition comprises a first copolymer having at least two or three silicon-bonded hydrolyzable groups. 1 monomeric hydrogen-containing silicon compound ("Precursor A"), Optionally at least zero, one, two or three hydrocarbyl radicals and compounds a second monomeric silicon compound having at least one hydrolyzable group bonded to the silicon atom of (i.e., "Precursor B"); Optionally, at least one functional group and at least one bonded to the silicon atom of the compound. A third monomeric silicon compound having a hydrolyzable group is used to hydrolyze the siloxane material. The functional group enhances solubility in the developer (i.e., "Precursor C"); Optionally, one or more additives are used to compound the siloxane materials into a stable composition in a suitable solvent system. A fourth precursor (i.e., “Precursor D”) based on a water-decomposable metal oxide precursor It is obtained by hydrolysis.

[0048] In one embodiment, precursor B is optionally mixed with one or more of precursors A, C and D. Used in conjunction with.

[0049] The ratio of precursors used in the present invention can be varied. Precursor A is 0-1 00mol%, precursor B is 0-50mol%, precursor C is 0-20mol%, precursor D is 0-50mol Precursors 1 and 2 can be used in an amount of at least 50 mol % of the composition, particularly at least It constitutes at least 60 mol %, for example at least 70 mol %.

[0050] The siloxane composition may be prepared by carrying out the hydrolysis and condensation in the same reaction vessel or separately. These precursors can be obtained by carrying out the processes separately in specific areas.

[0051] By selecting the relative amounts of the precursors, the silanes in the polyhydridosilsesquioxane resin can be The nol content can be adjusted.

[0052] The present invention relates to a poly(organosilane) obtained by hydrolyzing a first silicon compound having the formula II. It is particularly well suited for the preparation of compositions containing R 1 a -Si-R 2 b (II) Where: a is an integer of 1 or 2, b is an integer of 2 or 3; R 1 indicates a hydrogen atom, R 2 is a hydroxyl group, which may be independently selected from alkoxy, acyloxy, and halogen; Indicates a decomposable group.

[0053] In the sense of "halogen", each of the hydrolyzable groups is preferably independently chlorine or or bromine.

[0054] In the meaning of "alkoxy", each of the hydrolyzable groups preferably independently has 1 to Alkoxy groups having 6, in particular 1 to 4, carbon atoms, such as methoxy, ethoxy, n- propoxy, i-propoxy, butoxy, sec-butoxy, or tert-butoxy; In the meaning of "acyloxy", an acyl group has 1 to 4 carbon atoms. As a hydrolyzable group, each acyloxy is preferably independently acetoxy, acryloyloxy, It represents acryloxy or methacryloxy.

[0055] Specific examples of such precursors are triethoxysilane (HTEOS), trimethoxysilane (H TMOS), diethoxysilane and trichlorosilane.

[0056] The present invention also relates to a method for preparing a first silicon compound having the formula II with a precursor having the formula III. The present invention relates to a composition comprising a copoly(organosiloxane) obtained by hydrolysis, R3 m -SiR 2 n -R 4 o (III) Where: R 3 and R 4 is an alkyl group, an aryl group, an aralkyl group, a halogenated alkyl group, a halo aryl halide groups, aralkyl halide groups, organic groups having epoxy groups, mercapto groups , alkoxyaryl group, acyloxyaryl group, isocyanurate group, hydroxy group , a cyclic amino group, or a cyano group, or a combination thereof. Can, R 2 and R 3 may be an alkoxy group, an acyloxy group, or a halogen group; m is an integer from 0 to 1; n is an integer from 2 to 4; o is an integer from 0 to 1; The sum of m+n+o must not exceed 4.

[0057] The present invention further relates to a method for preparing a silicon compound having the formula II by hydrolysis of a first silicon compound having the formula II with a precursor having the formula IV. The composition includes a copoly(organosiloxane) obtained by decomposition, Z x -R 5 y -SiR 2 n -R 6 z (IV) Where: Z is a hydroxyl group, a carboxylic acid, a mercapto group, an amine or its salt, or a soluble group in an aqueous developer. groups such as quaternary ammonium salts that promote decomposition, R 5 is a spacer group covalently bonded to both Z and Si, and can be an alkyl group, an aryl group, or an aryl group. Ralalkyl groups, halogenated alkyl groups, halogenated aryl groups, halogenated aralkyl groups, an alkenyl group, an alkoxyaryl group, an acyloxyaryl group, or a combination thereof; and R 6 is an alkyl group, an aryl group, an aralkyl group, a halogenated alkyl group, a halogenated aryl group, Organic groups having an alkyl group, a halogenated aralkyl group, an epoxy group, a mercapto group, an alkoxy group, From aryl groups, acyloxyaryl groups, hydroxyl groups, cyclic amino groups, or cyano groups can be selected independently.

[0058] R 2 may be an alkoxy group, an acyloxy group, or a halogen group, y is an integer from 0 to 2; n is an integer from 1 to 3; z is an integer from 0 to 11; Here, the sum of y+n+z must not exceed 4.

[0059] In the structure of formula IV, x is a spacer group R 3 indicates a value that can be included and must be 1 or greater. do not have.

[0060] In one embodiment, formula IV is a free or protected aliphatic or phenolic aryl group. It includes silicon species having hydroxy groups.

[0061] In one embodiment, formula IV is a free or protected aliphatic or phenolic carboxylate. It contains silicon species having carboxylic acid groups.

[0062] Finally, the present invention provides a method for preparing a first silicon compound having the formula II, the first silicon compound having the formula V: R 7 p -MR 8 q (V) A composition comprising a copoly(organosiloxane) obtained by hydrolysis of a precursor having the formula: Regarding R 7 is an alkyl group, an aryl group, an aralkyl group, a halogenated alkyl group, a halogenated aryl group, Aryl group, halogenated aralkyl group, alkenyl group, alkoxyaryl group, acyloxyl group a aryl group, a cycloalkyl ... M represents a precursor that can be hydrolyzed and condensed to a metal oxide or metal-oxohydroxide. and may be independently selected from any metal capable of being formed into p is an integer from 0 to 1, M is capable of forming a stable carbon-metal bond; q is M ox -p is an integer number obtained from M ox is the oxidation state of the metal precursor, p is a carbon radical R covalently bonded to the metal precursor 7 is the number of R 8 is an alkoxy group, an acyloxy group, a halogen atom, which acts as a bond to other metal atoms. group, a hydroxyl group or an oxygen atom, or R 8 is a binary or coordinate ligand of the metal It is also necessary that the

[0063] In the text, "alkyl group" means C 1‐10 Alkyl groups, especially C 1‐4 represents an alkyl group, "Alkoxy group" is C 1‐10 Alkoxy groups, especially C 1‐4 represents an alkoxy group, An "aryl group" is a group having 1 to 5 rings, which are fused or conjugated, and 4 to 30 carbon atoms. "R" refers to an aromatic ring group having 1 to 5 carbon atoms.

[0064] The term "aralkyl group" refers to an aromatic ring group having 1 to 5 ring substituents and 4 to 30 carbon atoms. The substituents 1 to 6 each preferably have a carbon number of 1 to 10, and the alkyl groups 1 to 3 each preferably have a carbon number of 1 to 10. represents an aromatic ring group having 1 to 4 carbon atoms; "Alkoxyaryl" refers to an aryl group having 1 to 5 rings and 4 to 30 carbon atoms and ring-substituted The aryl group has 1 to 6 alkoxy groups as a group, and the alkoxy group has 1 to 10 , preferably having 1 to 4 carbon atoms, "Acyloxyaryl" refers to an aryl group having 1 to 5 rings and 4 to 30 carbon atoms, An aryl group having 1 to 6 acyloxy groups as a substituent, Contains 4 carbon atoms.

[0065] Examples of halogen substituents include fluoro, chloro, bromo and iodo groups.

[0066] Typically, the metal compounds of formula V are metal β-diketones or β-ketoesters or It's a combination of those.

[0067] The metal in the sense of "M" is typically selected from the group of transition metals and rare earth metals. Examples of metals include antimony, bismuth, germanium, halide, and chromium in various degrees of oxidation. Furan, iron, molybdenum, cerium, lanthanum, yttrium, tin, titanium, zirconium nium and tungsten, for example, zirconium, hafnium, aluminum Examples of suitable materials include aluminum, titanium and tin, and combinations thereof.

[0068] In particular, the metals are antimony(III), bismuth(III), germanium, hafnium(IV ), iron(III), molybdenum(V), cerium(IV), lanthanum(III), yttrium(I II), tin(IV), titanium(IV), zirconium(IV) and tungsten(V) You can choose from the following.

[0069] Specific examples of precursor II include tetramethoxysilane, tetrachlorosilane, and tetraacetamide. thoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane methoxysilane, tetra-n-butoxysilane, methyltrimethoxysilane, methyltriethoxysilane silane, methyltrichlorosilane, methyltriacetoxysilane, methyltripro Methyl tributoxysilane, methyl triphenoxysilane, methyl triphenyloxysilane N-phenyloxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, phenyl Trimethoxysilane, phenyltrichlorosilane, phenyltriacetoxysilane, phenyl Nyltriethoxysilane, γ-chloropropyltrimethoxysilane, γ-chloropropyl Triethoxysilane, γ-chloropropyltriacetoxysilane, 3,3,3-trifluoro Propyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, β -Cyanoethyltriethoxysilane, chloromethyltrimethoxysilane, chloromethyltrimethoxysilane Dimethyldimethoxysilane, phenylmethyldimethoxysilane, dimethysilane Tyldiethoxysilane, phenylmethyldiethoxysilane, γ-chloropropylmethyldi Methoxysilane, γ-chloropropylmethyldiethoxysilane, dimethyldiacetoxysilane silane, γ-glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane α-glycidoxyethyltrimethoxysilane, α-glycidoxyethyltriethoxysilane Silane, β-glycidoxyethyltrimethoxysilane, β-glycidoxyethyltriethylene α-Glycidoxypropyltrimethoxysilane, α-Glycidoxypropyltrimethoxysilane β-glycidoxypropyltrimethoxysilane, β-glycidoxypropyltrimethoxysilane γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, Glycidoxypropyltriethoxysilane, Glycidoxypropyltripropoxysilane, γ-Glycidoxypropyl tributoxysilane, γ-Glycidoxypropyl triphenoxysilane Silane, α-glycidoxybutyltrimethoxysilane, α-glycidoxybutyltriethylene , β-glycidoxybutyltriethoxysilane, γ-glycidoxybutyl Trimethoxysilane, γ-glycidoxybutyltriethoxysilane, δ-glycidoxybutyl butyltrimethoxysilane, δ-glycidoxybutyltriethoxysilane, (3,4-epoxy Cyclohexyl)methyltrimethoxysilane, (3,4-epoxycyclohexyl)methyl Triethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane , β-(3,4-epoxycyclohexyl)ethyltriethoxysilane, β-(3,4-epoxy β-(3,4-epoxycyclohexyl)ethyltripoxysilane ) Ethyl tributoxy silane, γ-(3,4-epoxycyclohexyl) propyl trimeth xysilane, γ-(3,4-epoxycyclohexyl)propyltriethoxysilane, δ- (3,4-epoxycyclohexyl)butyltrimethoxysilane, δ-(3,4-epoxycyclohexyl) (hexyl) butyl triethoxy silane, glycidoxymethyl methyl dimethoxy silane, Glycidoxymethyl methyldiethoxysilane, α-glycidoxyethyl methyldimethoxy Silane, α-glycidoxyethylmethyldiethoxysilane, β-glycidoxyethylmethyl β-glycidoxyethyl ethyl dimethoxysilane, α-glycidoxy Dipropylmethyldimethoxysilane, α-glycidoxypropylmethyldiethoxysilane , β-glycidoxypropylmethyldimethoxysilane, β-glycidoxypropylethyl Dimethoxysilane, glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropyl propylmethyldiethoxysilane, gamma-glycidoxypropylmethyldipropoxysilane, γ-Glycidoxypropylmethyldibutoxysilane, γ-Glycidoxypropylmethyldibutoxysilane Phenoxysilane, γ-glycidoxypropylethyldimethoxysilane, γ-glycidoxy Dipropylethyldiethoxysilane, γ-glycidoxypropylvinyldimethoxysilane , γ-glycidoxypropylvinyldiethoxysilane, and phenylsulfonylamino Examples of suitable silanes include, but are not limited to, propyltriethoxysilane.

[0070] Specific examples of the precursor III include, but are not limited to, 4-acetoxyphenylethyl triacetate. Chlorosilanes, 4-acetoxyphenylethyltrimethoxysilane, 4-acetoxyphenyl Triethoxysilane, 4-(acetoxyphenylethyl)methyldichlorosilane, 4 -(Acetoxyphenylethyl)methyldimethoxysilane, 4-(Acetoxyphenylethyl)methyldimethoxysilane (ethyl)methyldiethoxysilane, triethoxysilylpropylcarbamate, triethoxy Silylpropylmaleamic acid, N-(3-triethoxysilylpropyl)-4-hydroxy N-(3-triethoxysilylpropyl)gluconamide, (3-triethoxysilylpropyl)gluconamide (xysilyl)propyl succinic anhydride, ureidopropyltriethoxysilane, ureido Propyltrimethoxysilane, 3-hydroxy-3,3-bis(trifluoromethyl)propyl triethoxysilane, 4-(methoxymethoxy)trimethoxysilylbenzene and 6- (Methoxymethoxy)-2-(trimethoxysilyl)naphthalene.

[0071] Specific examples of precursors IV include antimony(III) alkoxides such as antimony(III) ethoxide. Bismuth(III) alkoxides such as bismuth(III) isopropoxide, bismuth(III) alkoxides, Germanium alkoxides such as tetraethoxygermane, hafnium(IV) butoxide, etc. Any hafnium(IV) alkoxide, iron(III) ethoxide, or other iron(III) alkoxide , molybdenum(V) alkoxides such as molybdenum(V) ethoxide, cerium(IV) iso Cerium(IV) alkoxides such as lanthanum(III) isopropoxide, etc. Which lanthanum(III) alkoxide, yttrium(III) isopropoxide, tin(IV) Alkoxides such as yttrium(III) alkoxides, tetra-t-butoxytin, tetra Alkyl and aryl substituted tin(IV) alkoxides such as la-i-propoxytin, Titanium(IV) alkoxides such as titanium(IV) butoxide and titanium(IV) isopropoxide. Zirconium oxide, zirconium(IV) butoxide, tungsten(V) alkoxide, etc. Tungsten(IV) alkoxide, tungsten(V) ethoxide and tungsten(VI) ethoxide and the like. However, the present invention is not limited to these.

[0072] In one embodiment, the method for producing the partially condensed polyhydridosilsesquioxane resin comprises the steps of: This involves using EOS (HSi(OC2H5)3) or a mixture of HTEOS with other trifunctional silanes. , which are subjected to a controlled hydrolysis / condensation reaction.

[0073] In such a method, the trifunctional silane is typically a methyltrimethoxysilane. Silane (MTMOS), methyltriethoxysilane (MTEOS), trimethoxyethylsilane ( ETMOS) or diethoxydimethylsilane (DMDEOS) or trimethoxyphenylsilane (PhTMOS).

[0074] In one embodiment, the monomers are dissolved in MeOTHF, which is used as the solvent for the synthesis. Alternatively, other solvents such as EtOTHF or a mixture of MeOTHF and EtOTHF, or R = 3-1 The two carbon synthesis solvents MeOTHF, EtOTHF, or R-OTHF are used.

[0075] In one embodiment, the controlled hydrolysis of the monomer is achieved by using a concentration in the range of 0.0001 M to 1 M. The acid solution may be obtained with a molar ratio ranging from 0.1 to 1.0.

[0076] According to one embodiment, the hydrolysis and polymerization are carried out entirely without a solvent, or The reaction is carried out in an organic solvent, such as an alcohol, an ester, a ketone, or an ether.

[0077] Specifically, suitable solvents include acetone, ethyl methyl ketone, methanol, and ethanol. , isopropanol, butanol, methyl acetate, ethyl acetate, propyl acetate, butyl acetate and tetrahydrofuran. Particularly suitable solvents are ketones and ethers, especially In some cases, there is a stabilizing effect due to coordination with silicon atoms during hydrolysis. Such examples are ethyl methyl ketone, methyl tetrahydrofurfuryl ether and ethyl ketone. ethyl tetrahydrofurfuryl ether.

[0078] The controlled hydrolysis of the monomers is carried out with the aid of acids having molar ratios ranging from 0.0001M to 1M or is obtained by addition of a base solution.

[0079] Organic or inorganic acids can be used in the synthesis.

[0080] Nitric acid, sulfuric acid, hydrochloric acid, hydroiodic acid, hydrobromic acid, hydrofluoric acid, boric acid, perchloric acid, carbon Acid, inorganic acids such as phosphoric acid, etc. can be used. Preferably, nitric acid or hydrochloric acid is used. is used due to its low boiling point, which simplifies purification of the product.

[0081] Alternatively, various organic acids can be used in place of the inorganic acids. The organic acids include: Carboxylic acid, sulfonic acid, alcohol, thiol, enol, and phenol groups. Examples are methanesulfonic acid, acetic acid, ethanesulfonic acid, toluenesulfonic acid, formic acid, is oxalic acid.

[0082] The bases used in the synthesis can likewise be inorganic or organic. Typical inorganic bases and Metal hydroxides, carbonates, bicarbonates, and other salts that give rise to alkaline aqueous solutions. Examples of materials are sodium hydroxide, potassium hydroxide, cesium hydroxide, calcium hydroxide, Sodium carbonate, and sodium bicarbonate. On the other hand, organic bases are metal salts of organic acids ( Sodium acetate, potassium acetate, sodium acrylate, sodium methacrylate, benzoate sodium azide, etc.), line-arm branched or cyclic alkylamines (diaminoethyl Tan, putrescine, cadaverine, triethylamine, butylamine, dibutylamine ethylamine, tributylamine, piperidine, etc.), amidines and guanidines (8- Diazabicyclo(5.4.0)undec-7-ene, 1,1,3,3-tetramethylglucose anidines, 1,5,7-triazabicyclo[4.4.0]-dec-5-ene, phosph Azans (P1-t-Bu, P2-t-Bu, P4-t-Bu, etc.), and quaternary ammonium compounds ( Tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetra butylammonium hydroxide, etc.

[0083] The reaction mixture during the hydrolysis and condensation processes was maintained at a temperature ranging from -30°C to 170°C. It is possible.

[0084] Those skilled in the art will appreciate that lower reaction temperatures provide improved control of the reaction, but at the expense of longer reaction times. On the other hand, excessive heat and proper control can make the process too fast. I know that.

[0085] A reaction temperature of 0 to 100° C. and a reaction time of 1 to 48 hours or 2 to 24 hours are preferred.

[0086] The method according to the present invention comprises the step of preparing a partially soluble organosiloxane polymer in an organic solvent system. The crosslinked, optionally metal, polymer has a viscosity of about 1000 MPa, as measured against a polystyrene standard. having a molecular weight of 5.00 to 100,000 g / mol, in particular about 1000 to 50,000 g / mol do.

[0087] Another embodiment of the present invention is where the solvent in which the hydrolysis and polymerization takes place contains some form of stable The solvents have improved the coating performance and product storage properties of the materials while at the same time improving the Regarding this, it is after the polymerization has been changed.

[0088] The stabilizing organic solvent system may be, for example, an organic ether, optionally mixed with other co-solvents or co-solvents. is formed by.

[0089] In one embodiment, the organic ether generally contains from 4 to 26 carbon atoms and optionally contains a hydroxyl group. The ethers may be linear, branched or cyclic, containing other functional groups such as

[0090] Particularly preferred examples are 5- and 6-membered ring ethers which may have a substituent on the ring.

[0091] Other suitable ethers are, for example, (C1-20)alkanediol(C1-6)alkyl Examples of the alkanediol alkyl ethers are propylene glycol. Monomethyl ether, propylene glycol dimethyl ether, propylene glycol n -butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol Dimethyl ether, dipropylene glycol n-butyl ether, tripropylene glycol glycerol monomethyl ether and mixtures thereof.

[0092] Particularly preferred examples of the ether are methyl tetrahydrofurfuryl ether, tetrahydrofuryl ether, Furfurfuryl alcohol, propylene glycol n-propyl ether, dipropylene glycol Lithium dimethyl ether, propylene glycol n-methyl ether, propylene glycol Cholesterol n-ethyl ether and their mixtures.

[0093] The stabilizing solvent system is a solvent containing only the types of ethers identified above, or Typical reaction media or other solvents such as propylene glycol monomethyl ether acetate. The proportion of ether in such a case is: It is about 10 to 90% by weight, particularly about 20 to 80% by weight, of the total amount of the solvent.

[0094] The solids content of the radiation sensitive formulation consisting of the selected solvent and resin material is 0.1% to 5 It is in the range of 0%, and preferably in the range of 0.5% to 10%.

[0095] In one embodiment, the formulations were subjected to various photoacid generation in a condensed deuterated esquinoxane resin. Combined with photobase generators and photosensitizers, it produces EUVL negative tone resists. and use it.

[0096] The solids content (or polymer content) controls the film thickness obtained during the coating process. It is used to

[0097] To improve the coating performance in terms of coating uniformity, silicon or fluorine Different surfactants, such as cyclohexane surfactants, were used to prepare silanol-containing polyhydric silsesquioxanes. The surface tension of the coating of the sukioxane formulation can be reduced. The use of an active agent can improve the coating quality if necessary. The amount is 0.001% by mass or less compared to the amount of the silanol-containing polyhydridosilsesquioxane. The range is from 10% by mass to 10% by mass.

[0098] The compositions may also contain salts, especially inorganic salts.

[0099] In one embodiment, the siloxane prepolymer solution has a viscosity of about 0.5 centipoise (cP) to about 1 The organic liquid has a flash point of at least 10°C and a viscosity of less than about 10 kPa. It may have a vapor pressure of 20°C.

[0100] As mentioned above, the radiation sensitive metal and silanol-containing polyhydric The silsesquioxane compositions are useful for the direct formation of desired inorganic material structures within devices. and / or as a radiation patternable inorganic resist to replace organic resists In either case, significant processing improvements can be utilized and patterned The structure of the material can also be improved.

[0101] The presence of silanol moieties in HSQ resin significantly improves the patterning ability of the coating compared to HSQ resin. Improve to.

[0102] The metal and silanol-containing polyhydridosilsesquioxane solutions are generally prepared in non-aqueous solvents. It provides high resolution patterning in a solution with good radiation sensitivity. The radiation patternable coating has a high degree of stability for formation of a radiation patternable coating.

[0103] The coating formed from the metal and silanol-containing polyhydridosilsesquioxane solution was It provides excellent direct patterning for the formation of patterned silicon oxide films. In some embodiments, exposure to radiation selectively removes the irradiated coating material. The developer composition is converted into a material that is resistant to removal so that the photoresist can be removed by the developer composition.

[0104] Thus, the coating can be negatively patterned. By selectively removing at least a portion of the coating material, areas of the coating are removed. After development of the irradiated coating, a pattern can be left behind that exposes the underlying substrate. Patterned silicon oxide materials have been shown to be useful in device fabrication with excellent pattern resolution. The coating material can be used to facilitate processing in extreme ultraviolet light, Designed to be sensitive to selected radiation such as ultraviolet light and / or electron beams Additionally, the precursor solution can be designed to be stable with a suitable shelf life for commercial sale. It can be formulated.

[0105] Radiation sensitive coating materials as negative radiation patterning coatings In negative patterning, exposure to radiation causes the irradiated coating to The coating material is more susceptible to removal by the developer composition compared to the non-irradiated coating material. By selectively removing at least a portion of the coating material, the coating material is converted into a material that is more resistant to oxidation. When removed, it leaves a pattern in which areas have been removed to expose the underlying substrate.

[0106] The formation of integrated electronic devices and the like generally involves the formation of individual elements or components within a structure. This involves patterning a material to induce desired functionality. and / or a method for applying a coating of different layers of laminated materials to the laminated materials, the coating being applied to selected portions of the laminated layers that interface with each other vertically and / or horizontally. The composition may include

[0107] The various materials may include selected dopants, dielectrics, electrical conductors and / or other types of materials. In order to form high resolution patterns, the semiconductor may include a material having a high resolution. The pattern can be introduced using radiation-sensitive organic compositions, some of which include The present invention is based on the concept of enabling selective material removal to be used to introduce selected patterns. The composition is called a resist because it is engineered to be resistant to imaging / etching. can be done.

[0108] The resist is then exposed to radiation having a selected pattern or a negative pattern. Exposing to light to form a pattern or latent image having developer-resistant and developer-soluble areas It is possible.

[0109] During similar irradiation processes such as EUV or e-beam, SiH species react to form intermediate reactive silicon This intermediate is highly reactive to the subsequent reaction due to the presence of moisture in the air or increased irradiation. In fact, many of the metal resists proposed for EUVL require reactive intermediates that are for the subsequent reaction that crosslinks the material to produce the molybdenum-type resist coating material. This shows the same problem of requiring moisture. Thus, the intermediate reaction generated by EUV from SiH It was found that the introduction of an appropriate amount of silanol groups in the film reacted directly with reactive silicon species.

[0110] As a result, silanol-containing polyhydridosilsesquioxanes have not been reported in the literature to date. It exhibits higher sensitivity in EUV lithography compared to previously available

[0111] In view of the above, the present technology provides a method for forming a resist undercoat film on a semiconductor substrate, comprising: and baking the composition to form a resist film.

[0112] In one embodiment, A resist primer or several primers are applied onto a semiconductor substrate and the composition is baked to form a forming one or more resist undercoats; The composition according to claim 1 is applied as a resist onto one or more resist undercoats to form a resist film. forming a stoichiometric film; exposing the resist film to light; After exposure, developing the resist film to form a resist pattern; Etching the resist underlayer using the resist pattern; The resist film thus patterned and the resist pattern thus patterned are forming a semiconductor substrate using the silicon substrate and a silicon underlayer; A method for manufacturing a semiconductor device is provided, comprising:

[0113] In one embodiment, forming an organic undercoat film on a semiconductor substrate; A composition for forming a resist film is applied onto an organic undercoat film, and the composition is baked to form a resist film. forming a fluorine film; exposing the resist film to light; After exposure, developing the resist film to form a resist pattern; Etching the resist underlayer using the resist pattern; The resist underlayer thus patterned is used to etch the organic underlayer. And, producing a semiconductor substrate using the organic undercoat film patterned in this manner; A method for manufacturing a semiconductor device is provided, comprising:

[0114] The present technique also provides a method of manufacturing a semiconductor device, the method comprising: A resist primer or several primers are applied onto a semiconductor substrate and the composition is baked to form a forming one or more resist undercoats; The composition according to claim 1 is applied as a resist onto one or more resist undercoats to form a resist film. forming a stoichiometric film; exposing the resist film to light; After exposure, developing the resist film to form a resist pattern; Etching the resist underlayer using the resist pattern; The resist film thus patterned and the resist pattern thus patterned are forming a semiconductor substrate using the silicon substrate and a silicon underlayer; include.

[0115] Additionally, a method for manufacturing a semiconductor device includes: forming an organic undercoat film on a semiconductor substrate; A composition for forming a resist film is applied onto an organic undercoat film, and the composition is baked to form a resist film. forming a fluorine film; exposing the resist film to light; After exposure, developing the resist film to form a resist pattern; Etching the resist underlayer using the resist pattern; The organic underlayer film is etched using the resist underlayer film thus patterned. And, producing a semiconductor substrate using the organic undercoat film patterned in this manner; The steps include:

[0116] The composition of the coating also has a large impact on other properties required for an EUVL resist material. For practical reasons, a sufficiently long post-coating delay (PCD) is necessary. or conventional lithography steppers and skimmers using nitrogen blankets. Unlike the conventional EUVL scanner, the EUVL scanner irradiation is carried out in a vacuum. Migration from the interface through the barrier or from an independent resist track can take a long time. Therefore, the coating composition is stable during these steps in the gas exhaust chamber. As it should be.

[0117] Therefore, the material should exhibit sufficient PCD stability, which is sufficient to prevent any The coating can be easily removed using a solvent or developer without leaving any residue. Surprisingly, the correlation between Si-H and Si-OH in the film has a significant effect on PCD stability. It was found that too high a Si-OH content in the film leads to premature crosslinking of the material. If the curing time in the patterning process is too long, the unexposed areas may develop. FTIR is a quick and easy tool to assess the Si-H to Si-OH ratio. At certain ratios, the material provides high resolution patterns, low LER and good PCD stability. It was observed that.

[0118] Specifically, the chemical structure of the synthetic silanol-containing polyhydridosilsesquioxane shown in FIG. To verify the structure, FTIR spectra were recorded.

[0119] As can be seen from this figure, silanol-containing polyhydridosilsesquioxane is 3200-3700cm due to the silanol network structure ‐1 A strong and broad Si-OH peak in the range Furthermore, the Si-H functionality is at about 2248 cm ‐1 It is considered to be a sharp peak centered on Therefore, the peak height ratio of Si-H to Si-OH is preferably at least More often than 4:1, but less than 100:1 at most, or more preferably more than 3:1 It should be less than 50:1.

[0120] The invention relates to the use of the described compositions in the formation of patterns on semiconductor substrates.

[0121] Next in the drawing, FIG. 1 shows a substrate surface 10 coated with an organic underlayer 12, followed by a typical An inorganic intermediate layer 14, typically made of a high silicon-containing material, is coated and cured. 1 shows a typical process currently used. On top of that, a photoresist 16 is coated. will be displayed.

[0122] After irradiation 18 using a 193 nm wavelength as is commonly known, a pattern is formed and developed. Such layer combinations are frequently referred to in the literature as "three-layer" stacks, referring to the number of layers. In order to transfer the pattern formed on the photoresist to a substrate, After that, a commonly known pattern transfer etching process can be applied. (Figure 1).

[0123] Note that the stack of various layers used in lithography can exceed three It's worth it.

[0124] Another commonly used layer combination is the 4-layer stack (see FIG. 2), where the organic An undercoat layer (or substrate) 12 is applied first, followed by a thin layer, typically made of a high silicon-containing material. On top of this, the four-layer stack of FIG. Before completing the photoresist 16, an organic bottom anti-reflective 18 layer is applied.

[0125] Those familiar with the art of underlying materials used in photoresist patterning will understand all The described underlayers can be coated and cured, as well as vapor deposited ( by vapor deposition processes such as chemical vapor deposition (CVD), atomic layer deposition (ALD) and similar methods I know it can be done.

[0126] For those skilled in the art, the same procedures can be applied to 13.5 nm EUVL.

[0127] However, due to the absorption challenges, the probability distribution of both photoacid and photon irradiation, The typical CARs used face serious challenges, especially those related to LER and LWR.

[0128] Therefore, the number of layers is reduced, promising a simplified stack that reduces LER and LWR challenges. There has been considerable interest in using inorganic photoresists to The resist may be in the form of one or more readily hydrolyzable or hydrolyzed metal oxide precursors. The above compounds are made of metal oxides, and hydrogen silsesquioxanes. These advantages include Metal oxide resists provide unexpected EUVL dose sensitivity, while hydrogen silsesquioxane resists provide Polymers offer excellent resolution with low LER / LWR at very low EUVL sensitivity.

[0129] Therefore, both methods are difficult to use in EUVL patterning processes.

[0130] The present invention uses metal-silanol containing siloxanes as a preferred method for lamination. This achieves both simplification and a reduction in the amount of metal used in the patterning process. See Figure 3. Light.

[0131] In one embodiment of the present invention, the substrate 20 is a spin-on carbon or amorphous carbon layer in EUV. The thin film according to the invention 22 is in the form of a pin and is coated with a mainly organic coating 22. The patternable films are gold-containing polyhydridosilsesquioxane resins24. Based on silanols and silanols.

[0132] This coating has a higher sensitivity and is easier to pattern by EUVL compared to HSQ resins in the literature. and has significantly lower LER / LWR compared to CAR and inorganic resins described in the literature It is.

[0133] In particular, the present invention provides a means for high resolution patterning with a bilayer structure in the absence of metals. This provides a valuable advantage in producing fully functional transistor die without significant yield loss. This could be a significant advantage. Silicon-containing materials are well known for their relatively low absorption of EUV light. On the other hand, EUV generates unstable silanols from the Si-H moieties in the HSQ resin shown in Figure 4. It has been established that:

[0134] Based on the examples presented herein, it is possible to determine whether a gold nanoparticle can promote silanol condensation or SiH oxidation. Metal-containing additives are also beneficial in achieving lower sensitivity compared to methods described in the literature. It is clear that

[0135] Improvement is 1. Increased sensitivity of the resin compared to silicon containing resin alone, or 2. Accelerated condensation process compared to non-metal-containing formulations You can get more.

[0136] The present invention deposits a carbon-rich underlayer 22 on a surface 20 that is used in the manufacture of integrated circuits. The underlayer can be formed by a gas phase process such as CVD or by a stripping process. The coating is deposited by pin coating and curing. The composition according to the present invention is then applied. , which can be directly patterned by novel patterning techniques such as EUVL. This produces a silicon and metal rich oxide coating on the surface.

[0137] After application by spin coating or other suitable deposition method for the liquid, a pre-bake step is performed. This is done to remove solvents and volatile compounds contained in the coating material. This is necessary to avoid contamination of the manufacturing equipment.

[0138] Pre-baking is performed at different temperatures and times depending on the boiling temperature of the solvent and volatile components. Typically, pre-baking is performed at 60°C to 120°C for 30 seconds to a maximum of 30 minutes. It is possible to do so.

[0139] After drying or pre-baking, the EUV light, electron beam, or other suitable masking is applied. Exposure of the coating to a laser beam or similar exposure method (26) produces a pattern on the substrate. The dose required to generate the pattern is a minimum of 10 mJ / cm 2 in, Maximum 200mJ / cm 2 It is.

[0140] As mentioned earlier, RLS trade-offs, including reasonable throughput for industrial applications, For a variety of reasons, lower doses are preferred, including addressing the

[0141] A post-exposure bake is optionally performed after EUV exposure. This step increases the resist's Post-exposure baking can improve crosslinking of exposed areas resulting in contrast. It can be performed at a maximum temperature of 150°C for 30 seconds to 30 minutes.

[0142] The resist is developed to remove the unexposed areas to obtain the design pattern. The unexposed areas of 24 dissolve in the developer.

[0143] Tetramethylammonium hydroxide, with different mass ratios from 0.1% to 25%; Water commonly used in industry based on bases such as potassium hydroxide, sodium hydroxide, etc. The developer can be effectively used as a developer. This is done in a manner generally known by using a liquid solution spray or paddle. Alternatively, the substrate can be immersed in a bath of developer.

[0144] A curing step to densify the exposed and developed pattern may optionally be followed by a further To obtain a crosslinked material, or through a process where the material exhibits some reflow, the resist This process can be carried out to change the shape of the pattern. This process is prepared without a curing step. The curing can result in a more etch resistant material compared to that of the previously cured material. Curing can be done in 2 minutes at 400°C or less, within 30 minutes. This can be done by heating the coating placed in an oven.

[0145] Radiation-sensitive coatings contain a variety of photoacid generators (PAGs), photobase generators (PBGs), and sensitizers. Such additives are important components of the CAR and their probability distribution is often the root cause of LER issues in resist formulations.

[0146] In general, the photoacid generator and the photobase generator are non-ionic acid generators and non-ionic base generators. The photobase generator can be selected from a photosensitizer or an ionic type. They can be used in combination.

[0147] Surprisingly, no increase in LER was observed as a function of PAG or PBG but after exposure Due to the stochastic distribution problem and shot noise during irradiation, it is not possible to increase the LER without decreasing the required dose. Nonetheless, PAG or PBG were added to the coating formulation to Enhances acid or base catalyzed condensation of radiation sensitive coatings, potentially resulting in more densified It can facilitate condensation of the exposed areas of the film resulting in a pattern.

[0148] A wide variety of PAGs, PBGs and sensitizers are available. To name a few, PAGs include: , aryl diazonium salts, diaryl halonium salts, triaryl sulfonium salts, etc. The amount of ionic photoacid generators is determined by the amount of silanol-containing polyhydric The amount of the silsesquioxane is in the range of 0.001 to 10% by mass.

[0149] The various photoacid generators include nitrobenzyl esters, sulfones, phosphates, n-hydrides, and sulfonates of phenols, diazonaphthoquinones, Non-ionic acid generators such as halogen-containing compounds and iminosulfones. The amount of the acid generating portion is 0.00 compared to the amount of the silanol-containing polyhydridosilsesquioxane. The content is within the range of 1 to 10% by mass.

[0150] The photobase generator consists of Co(III)-amine and alkylamine salts, O-acyloximes, and bases. In the photobase generating section, benzyloxycarbonyl derivatives and formamide can be added. The amount is 0.001 to 10 mass % compared to the amount of silanol-containing polyhydridosilsesquioxane. Quantity %.

[0151] EUV lithography confirmed this theory, and scanning electron microscope (SEM) images of the patterns is shown in Figure 8.

[0152] Films were prepared using Polymer 1 with 2% solids as described in Example 1. The patterned image was obtained by irradiating the film with EUV light and finally developing it with 2.38% TMAH. As shown, for example, 65.4 mJ / cm 2 , 86.5mJ / cm 2 , 82 mJ / cm 2 With the amount of irradiation, High-resolution SEM images were obtained for various half-pitches of 22 nm, 30 nm, and 50 nm, respectively.

[0153] Furthermore, e-beam lithography was used to further confirm our theory. Three formulations with different contents of the polymer prepared in were used: 1%, 2%, and 3%. SEM image of 9 at 600 μC / cm 2 , 400μC / cm 2 , and 200 μC / cm 2 And the 50 nm line As can be seen, the sample with the higher solids content Higher sensitivity was observed for the silanolates in the film, which increased the crosslinking density and reactivity. This is because of the high content of ethanol.

[0154] However, when the ratio of SiH to SiOH is less than 4, as seen in samples 3 and 5, The amount of silanol in the film is too high. The self-crosslinking of SiO2 is relatively fast and cannot be removed by developer, making the PCD suitable for EUV. On the other hand, when the ratio of SiH to SiOH is greater than 100, the material does not show the above-mentioned properties (Figs. 5-6 and Table 1). Above this value, the sensitivity of the film decreases significantly and therefore a large EUV dose is required.

[0155] Therefore, a synthesis method was developed to adjust the amount of SiH / SiOH ratio in the resin by using different hydrolysis times. The approach was extensively investigated and / or in different solvents and / or with different monolayers. The reaction was carried out using the same mer ratio, and the FTIR results are shown in Figure 7.

[0156] In real EUV lithography applications, the post-coating of EUV resist film after soft baking is The polymer and formulation developed must have a PCD of at least 1 hour. Extensive PCD testing of the materials was performed and the procedures are summarized in Table 1.

[0157] X is the mark given to samples whose PCD is suitable for EUV lithography, while Y is Only good at low soft bake temperatures, 80 o C is good for only 1 minute, Z is , a soft bake temperature high enough to completely remove the solvent in the film is not acceptable. .

[0158] To further improve the sensitivity, metal oxide nanoparticles were added into the polymer solution to It can be used as a resist. Titanium oxide nanoparticles, hybrid titanium oxide nanoparticles Add different metal oxide nanoparticles, such as aluminum nanoparticles or hafnium nanoparticles. It can be added.

[0159] The results using e-beam lithography are shown in Figures 10a, 10c, and 10d. The addition of nanoparticles catalyzes the crosslinking reaction between silanols and silanols bearing Si-H. Another advantage is that the coating may increase the sensitivity of the membrane through its activity. Metal oxides, which are the etchants in plasma etching during microelectronics manufacturing, In addition, the addition of 2. Addition of a solubility enhancer such as HFIPTEOS with only 5 wt% significantly increased line edge roughness. It was found that the ZnO content increased significantly (SEM image in Figure 8c).

[0160] Based on the above, the following embodiments are provided: The precursor solution contains an organic liquid and is a compound that is substituted with Si-H or Si-R in the silicon-oxygen network. In comparison, about 0.001M to about 1M of silanols, or silicon-carbon bonds and silicon-hydrogen bonds and a viscosity of about 0.5 centipoise (cP) to about 150 cP. The precursor solution has a flash point of at least 10°C and a thermal expansion coefficient of less than about 10 kPa. It may have a vapor pressure of 0°C.

[0161] The polyhydridosilsesquioxane-coated substrate is exposed to radiation of specific wavelengths of light. A method for patterning metal and silanol in a selected pattern. The coated substrate is irradiated along the axial direction to separate the irradiated and unirradiated areas of the coating. forming an irradiated structure in the region of the irradiated pattern and selectively developing the irradiated structure and the unirradiated removing a substantial portion of the coating to form a patterned substrate. Hmm, a method.

[0162] Polyhydridosilsesquioxane is reacted with light of a specific wavelength, less than 13.5 nm, to produce a polyhydridosilsesquioxane. A method for patterning metal and silanol containing sun-coated substrates.

[0163] At any point along the coating, the average thickness is about 5 microns or less, and A coated substrate comprising a radiation sensitive coating having a thickness variation of about 50% or less. and the coating is a silicon-carbon bond and a silicon-hydrogen and / or silanol bond. It contains silicon-oxygen or silicon-oxygen-metal networks with bonds.

[0164] A substrate having a surface and a first coating at selected areas along the surface. A patterned substrate that includes a plurality of nanoparticles that are not present in other areas along the surface. The coating of 1 is a silicon-oxygen or silicon-carbon bond and a silicon-hydrogen and and / or a silicon-oxygen-metal network having silanol bonds. The first coating is soluble in at least some organic liquids or The coating is soluble in aqueous base.

[0165] A patterned substrate includes a substrate having a surface and a first The first coating is generally a 100% SiO2 coating, and is absent in other areas along the surface. The bonding is silicon-oxygen or silicon-carbon bond and silicon-hydrogen and / or silane bond. The silicon-oxygen-metal network with nodal bonds is formed, and the oxygen plating rate is less than 50 nm / min. It has an etch rate in the Zuma or ashing process.

[0166] The following non-limiting examples illustrate embodiments. Working Example

[0167] Gel permeation chromatography data was obtained using a Shodex KF column (KF-G; KF-80 3L; KF-802; KF-801) were collected on an Agilent 1260 Infinity LC. The temperature of the detector and column was kept at 40°C. The flow rate of the THF eluent was 1.0 ml / min. there were.

[0168] Chemical structures were analyzed by Fourier transform infrared spectroscopy (FT-IR) using a Bruker VERTEX 70. Film samples were used for the analysis.

[0169] Post-coating retardation (PCD) test: The polymer solutions from the examples were diluted with PGMEA and The polymer solution was spin-coated onto a silicon wafer at 1500 rpm for 30 seconds. Film samples were prepared by heating at temperatures ranging from 80°C to 150°C. A soft bake was performed on a hot plate for 1 min. The film was stored at room temperature for 1 h and then diluted with 2.38% TMA The film was developed with H, washed three times with deionized water, and dried with nitrogen gas.

[0170] The film thickness was measured before and after development to evaluate the PCD. After soft baking, the film was developed with TMAH. When the particles were completely removed, the PCD was good. The results are summarized in Table 1.

[0171] E-beam lithography was carried out on a Vistec tool. A 2% solid formulation was applied to the Spin coat onto silicon wafer via spin coater for 30 s at pinning speed Then, a soft bake was performed on a hot plate at 80°C for 1 minute. The e-beam dose was 100k. V, 100 to 900 μC / cm at 1 nA current2 The development process varies between 2. This was done by immersing the film in a 38% TMAH solution for 1 minute. The film was then deionized. It was washed three times with water and finally dried with nitrogen gas.

[0172] EUV Lithography: 2% solids polymer formulation, 1500 rpm spin speed for 30 seconds The mixture was spin-coated on a silicon wafer using a spin coater at 80° C. The film sample was soft-baked for 1 minute on a hot plate. The XIL-II EUV tool at the Paul Scherrer Institute in Villigen was used for irradiation. 150mJ / cm 2 The development process consisted of immersing the film in a 2.38% TMAH solution for 1 minute. The film was then washed three times with deionized water. The mixture was then dried with nitrogen gas.

[0173] Example 1 In one flask, 121.55 grams of triethoxysilane (HTEOS) was added to 234. Dissolved in 60 grams of methyl tetrahydrofurfuryl ether (MeOTHF). 58.65 grams of MeOTHF, 25.62 grams of deionized water (DIW) and 11.71 grams of 0. Mix 0.1 mole of nitric acid and 3 equal parts of the above HTEOS solution for 1.5 hours. After the addition was completed, the mixture was mixed for another 20 hours and the reaction was continued. Methyl ethyl ketone (MEK) was added to the polymer weight four times. The combined solution was filtered through a 0.2 micron filter. The data show a Mw of 5001, a Mn of 2239, and a polydispersity of 2.23.

[0174] The etching data for the polymer of Example 1 is shown in Table 1. The spin-on carbon (SO C) SOC300 manufactured by PiBond. Table 1. Etching data for the polymer prepared in Example 1

[0175] [Table 1]

[0176] Example 2 In one flask, 121.55 grams of HTEOS was mixed with 234.60 grams of ethyl tetrahydrofuran. The mixture was dissolved in 58.65 grams of EtOTHF, 25. Mix 62 grams of DIW and 11.71 grams of 0.01 mole nitric acid together. The HTEOS solution was added in three equal portions over a 5 hour period. After addition was complete, the reaction was further Mixing was continued for 20 hours. Evaporation was performed to obtain a solid content of 21-25%. MEK was added to the polymer weight. The resulting polymer solution was filtered through a 0.2 micron filter. The chromatography data showed a Mw of 7396, a Mn of 2903, and a probable NA of 2.54. It shows scattering.

[0177] Example 3 In one flask, 5.510 g of HTEOS and 10 g of Tet with a molar ratio of 90:10 were added. A quantity of 0.567 grams of trimethoxysilane (TMOS) was dissolved in 11.730 grams of MeOTHF. The mixture was dissolved in 2.932 grams of MeOTHF, 1.290 grams of DIW and 0.590 grams of Mix 0.01M nitric acid mixture and incubate the above HTEOS and TMOS solutions for 1.5 hours. The reaction was allowed to continue mixing for an additional 20 hours after addition was complete. The polymer was added 4 times to obtain a solid content of 21-25%. The solution was filtered through a 0.2 micron filter. Gel Permeation Chromatography Data exhibits a Mw of 4497, a Mn of 2059, and a polydispersity of 2.18.

[0178] Example 4 In one flask, 5.223 grams of HTEOS and 0.01 grams of ... 0.854 grams of TMOS was dissolved in 11.729 grams of MeOTHF. 2.930 grams of Me A mixture of OTHF, 1.290 g DIW and 0.590 g 0.01 mol nitric acid Mix and add in 3 equal portions to the above HTEOS and TMOS solutions for 1.5 hours. After the addition was completed, the mixture was mixed for another 20 hours and the reaction was continued. Evaporation was performed to obtain a solid content of 21-25%. MEK was added four times based on the weight of the polymer. The resulting polymer solution was filtered through a 0.2 micron filter. The gel permeation chromatography data was: Mw 2022, NA 1191. Mn, and a polydispersity of 1.69.

[0179] Example 5 In one flask, 3.154 grams of HTEOS and 2.2 grams of TMOS in a 50:50 molar ratio were added. A quantity of 93 grams was dissolved in 11.729 grams of MeOTHF. 2.930 grams of MeOTHF, Mix a mixture of 1.330 g DIW and 0.610 g 0.01 mol nitric acid. This was added in three equal portions to the HTEOS and TMOS solutions above over a period of 1.5 hours. After completion of the reaction, the reaction was continued for another 20 hours with mixing. Evaporation was performed to obtain a solid content of 21-25%. MEK was added four times based on the weight of the polymer. The resulting polymer solution was filtered through a 0.2 micron filter. The gel permeation chromatography data was: Mw 3359, NA 1669. Mn, and a polydispersity of 2.01.

[0180] Comparative Example 1 In one flask, 60.77 grams of HTEOS was dissolved in 117.25 grams of ethanol. Dissolved: 29.37 g ethanol, 6.40 g DIW and 2.93 g Mix 0.01 mol of nitric acid and 3 equal portions of the above HTEOS solution for 1.5 hr. After the addition was completed, the mixture was mixed for another 20 hours and the reaction was continued. 250 grams of PG Solvent exchange was performed by adding MEA and then evaporating the solvent to obtain a solid content of 21-25%. The polymer weight was added four times, and the resulting polymer solution was filtered through a 0.2 micron filter. Gel permeation chromatography data showed Mw of 16598, Mn of 8432, and and a polydispersity of 1.97.

[0181] Comparative Example 2 In one flask, 60.77 grams of HTEOS was dissolved in 117.25 grams of ethanol. Dissolved: 146.60 g ethanol, 6.40 g DIW and 2.93 g The HTEOS solution was mixed with 0.01 mol of nitric acid and incubated for 1.5 hours in three The mixture was added in equal portions. After addition was complete, the reaction was allowed to continue mixing for an additional 20 hours. Solvent exchange was performed by addition of 1-BuOH and solvent evaporation to give a solid content of 21-25%. The polymer solution was diluted with 0.2 ml of ethyl ethyl ketone (MEK) four times. The gel permeation chromatography data showed a Mw of 31. 88, Mn of 1967, and polydispersity of 1.62.

[0182] Polymer Testing The molecular weights of the polymers of Examples 14 to 18 on GPC were compared with those of the materials of Comparative Examples 1 and 2. Then, spin coat the polymer solution at 2% at a spinning speed of 1500 rpm for 30 seconds. Film samples were prepared from various polymers by the above method. The substrate was soft baked at a temperature in the range of °C for 30 seconds to 2 minutes.

[0183] The GPC data and post-coating retardation data for the materials are shown in Table 2. Table 2. GPC data and post-coating delay for materials produced with different compositions.

[0184] [Table 2]

[0185] Legend (for PCD results): X=80 o C / 1h and 150 o Good for at least 1h of PCD after firing at C / 1h, Y=80 o C / 1h later Y=Good, but 150 o Not good at C / 1h, Z=80 o C / 1h and 150 o Z=bad for both C / 1h. Note: For EUVL, the PCD time must be at least 1 hour for a safe exposure.

[0186] Evaluation of results: Example 1 demonstrates high-resolution patterning with low LER (Figure 5). Example 1 is also compared (Figure 6) with a similar material made with a lower silanol content (Comparative Example). On the other hand, if the silanol content is too high, the PCD performance is impaired. Therefore, it is preferable to use a material having Si—H and Si—OH peaks. The ratio of height ratio (Figure 7) should be more than 4 but less than 100, but not more than 3 but less than 50. More preferably, it is less than 100 .mu.m.

[0187] Example 6 Preparation of polymer solutions with HTEOS:HFIPTEOS=99:1 molar ratio In one flask, 5.941 grams of HTEOS and 0.5% ethanol with a molar ratio of 99:1 were added. 136 grams of 3-hydroxy-3,3-bis(trifluoromethyl)propyl triethylene Toxosilane (HFIPTEOS) was dissolved in 11.729 grams of MeOTHF. Mixture of 1.300 g EtOTHF, 1.300 g DIW and 0.590 g 0.01 mol nitric acid The mixture was mixed and added in three equal portions to the above HTEOS and HFIPTEOS solutions for 1.5 hours. After addition was complete, the reaction was allowed to continue mixing for an additional 20 hours. Evaporation was performed to obtain a solids content of 21-25%. %. MEK was added four times to the polymer weight. The resulting polymer solution had a 0.2 micron filter. The gel permeation chromatography data was: Mw 3970, pH 20. It exhibits a Mn of 23 and a polydispersity of 1.96.

[0188] Example 7 HTEOS:HFIPTEOS=97.5:2.5 molar ratio In one flask, 5.744 grams of HTEOS and HFIPTEO in a molar ratio of 97.5:2.5 0.334 grams of S was dissolved in 11.729 grams of MeOTHF. 2.930 grams of EtOTHF F, mix a mixture of 1.290 g DIW and 0.590 g 0.01 mol nitric acid. and added in three equal portions to the above HTEOS and HFIPTEOS solutions over a period of 1.5 hours. After the addition, the mixture was mixed for another 20 hours and the reaction was continued. After evaporation, the solid content was 21-25%. MEK was added four times based on the weight of the polymer. The resulting polymer solution was filtered through a 0.2 micron filter. Gel permeation chromatography data showed Mw of 3519, Mn of 1766. , and a polydispersity of 1.99.

[0189] Example 8 HTEOS:HFIPTEOS=95:5 molar ratio In one flask, 5.430 grams of HTEOS and 0.6 grams of HFIPTEOS in a molar ratio of 95:5 were added. 48 grams of 1.25g of MeOTHF was dissolved in 11.729 grams of EtOTHF. Mix 290 g DIW and 0.590 g 0.01 mol nitric acid mixture, 1 Add in 3 equal portions to the HTEOS and HFIPTEOS solutions above at 0.5 hours. Addition complete. The mixture was then mixed for another 20 hours and the reaction was continued. Evaporation was performed to obtain a solid content of 21-25%. was added to the polymer weight four times. The resulting polymer solution was filtered through a 0.2 micron filter. Gel permeation chromatography data showed Mw of 3069, Mn of 1569, and and a polydispersity of 1.95.

[0190] Example 9 HTEOS:HFIPTEOS=90:10 molar ratio In one flask, 4.855 grams of HTEOS and 1.223 grams of 90% molar ratio HFIPTEOS:10 was dissolved in 11.729 grams of MeOTHF. 2.930 grams of EtOTHF Mix a mixture of 1.290 g DIW and 0.590 g 0.01 mol nitric acid. and added in three equal portions to the above HTEOS and HFIPTEOS solutions over a period of 1.5 hours. After the addition, the mixture was mixed for another 20 hours and the reaction was continued. After evaporation, the solid content was 21-25%. MEK was added four times based on the weight of the polymer. The resulting polymer solution was filtered through a 0.2 micron filter. Gel permeation chromatography data showed Mw of 2661, Mn of 1524. , and a polydispersity of 1.74.

[0191] Example 10 Polymer 1 + HFIPTEOS = 97.5:2.5 mol The polymer prepared in Example 1 was diluted with PGMEA to obtain a 2% solids solution. The two solutions were added in a molar ratio of polymer 1:HFIPTEOS=97.5:2.5. Mix warm for 30 minutes. The final solution was then filtered through a 0.2 micron filter.

[0192] Polymer Testing The molecular weights of the polymers of Examples 1 and 6 to 9 were measured on GPC. The rubber samples were spin-coated with 2% polymer solution at a spinning speed of 1500 rpm for 3 h. Then, soft bake was performed at a temperature range of 80°C to 150°C for 30 seconds to 2 minutes. Ta.

[0193] The GPC data and post-coating retardation data for the materials are shown in Table 3. Table 3. GPC data and post-coating delay for materials produced with different compositions.

[0194] [Table 3]

[0195] Legend (for PCD results): X=80o C / 1h and 150 o Good for at least 1h of PCD after firing at C / 1h, Y=80 o Good after C / 1h, but not good at 150C / 1h. Z=80 o C / 1h and 150 o Both C / 1h are defective. Note: For EUVL, the PCD time must be at least 1 hour for a safe exposure.

[0196] Evaluation of the results. Examples 6 to 9 show the effect of the functional group in increasing the solubility in the developer. As shown in Figure 8, the addition of functional groups further reduces the radiation dose required to obtain a pattern. Moreover, the use of such functional groups reduces the cost of the process and has environmental and health benefits. A less concentrated developer solution can be used, which reduces the risk of developing resin. The lipid composition can be obtained by hydrolyzing the precursors separately or simultaneously. The following is shown (Examples 6 to 9).

[0197] Example 11 HTEOS:MTEOS=90:10 molar ratio In one flask, 5.423 grams of HTEOS and 0.01 grams of ... .654 grams of methyltriethoxysilane was dissolved in 11.729 grams of MeOTHF. 2.930 g EtOTHF, 1.290 g DIW and 0.590 g 0.01 The HTEOS and MTEOS solutions were mixed with a mixture of 1.5 moles of nitric acid and incubated for 1.5 hours. The mixture was added in equal portions. After addition was complete, the reaction was allowed to continue for an additional 20 hours with mixing. The resulting polymer solution had a form content of 21-25%. MEK was added to the polymer four times by weight. The gel permeation chromatography data was obtained by filtration through a 2 micron filter. It exhibits a Mw of 25, a Mn of 1277, and a polydispersity of 1.97.

[0198] Example 12 HTEOS:DMDEOS=90:10 molar ratio In one flask, 5.524 grams of HTEOS and 0.018 grams of ... .554 grams of dimethyldiethoxysilane (DMDEOS) to 11.729 grams of MeOTHF Dissolve: 2.930 g EtOTHF, 1.290 g DIW and 0.590 g Mix a mixture of 0.01 mol of nitric acid and add it to the above HTEOS and DMDEOS solution for 1.5 hr. After addition was complete, the reaction was allowed to continue for an additional 20 hours with mixing. The polymerization was carried out to obtain a solid content of 21-25%. MEK was added to the polymer four times. The combined solution was filtered through a 0.2 micron filter. Gel permeation chromatography The data indicates a Mw of 2207, a Mn of 1148, and a polydispersity of 1.92.

[0199] Example 13 HTEOS:PhTMOS=90:10 molar ratio In one flask, 5.359 grams of HTEOS and 0.01% ethanol with a molar ratio of 90:10 were added. 0.719 grams of PhTMOS was dissolved in 11.729 grams of MeOTHF. A mixture of 0.01 mol EtOTHF, 1.250 g DIW and 0.570 g nitric acid Mix and add in three equal parts to the above HTEOS and PhTMOS solutions for 1.5 h. After the addition was completed, the mixture was mixed for another 20 hours and the reaction was continued. Evaporation was performed to obtain a solid content of 21-25%. Methyl ethyl ketone (MEK) was added four times based on the weight of the polymer. The gel permeation chromatography data was obtained by filtration through a 0.2 micron filter. It exhibits a Mw of 1930, a Mn of 746, and a polydispersity of 2.59. Evaluation of the results Examples 11 to 13 were used to copolymerize with HTEOS or other hydrogen-containing precursors. The effects of some other monomers that can be used are shown.

[0200] Example 14 Polymer 1 + titanium oxide = 98:2% by weight Titanium oxide nanoparticles were prepared using titanium(IV) isopropoxide (TIIP, 15.887 g) was synthesized by dissolving in isopropanol (200 g). (5.033 g), acetic acid (3.357 g), and IPA (200 g) were added to a separate mixture. The reaction was carried out at room temperature for 6 hours, and then the reaction mixture was added with PG ME (500 grams) was added and the IPA was removed from the solution via rotary evaporator. Solvent Evaporation The resulting solution was filtered through a 0.2 micron filter to obtain a 2% solid solution. The polymer prepared in Example 1 was then diluted with PGMEA to a concentration of 2%. A solution was obtained. The amount of titanium oxide nanoparticles was adjusted to a mass ratio of polymer 1:TiOx=98:2% by weight. The two solutions were mixed at room temperature for 30 minutes. The mixture was filtered through a filter.

[0201] Example 15 Polymer 1 + titanium oxide = 95:5% by weight The sample preparation process was the same as in Example 17, except that the amount of titanium oxide added was 5% by weight. It is.

[0202] Example 16 Polymer 1 + titanium oxide = 90:10% by weight The sample preparation process was the same as in Example 15, except that the amount of titanium oxide added was 10% by weight. It seems that.

[0203] Example 17 Polymer 1 + titanium aluminum oxide = 97:3% by weight The polymer prepared in Example 1 was diluted with PGMEA to obtain a 2% solids solution. The amount of aluminum nanoparticles was polymer 1: titanium aluminum oxide = 97:3 by mass ratio. The two solutions were allowed to mix for 30 minutes at room temperature. The liquids were then filtered through a 0.2 micron filter. The mixture was filtered through a filter.

[0204] Example 18 Polymer 1 + titanium aluminum oxide = 90:10% by weight Titanium aluminum oxide nanoparticles were synthesized using TIIP and aluminum isopropoxide (AlOi The reaction was carried out by controlled hydrolysis / condensation of Pr. In this study, a mixture of TIIP (27.831 g) and AlOiPr (5 g) was dissolved in IPA (320 g). The Ti:Al molar ratio is 8:2. In a separate flask, add 8.377 grams of water, 7.350 grams of A mixture of 200 grams of acetic acid and 200 grams of IPA was mixed in a second flask. was added dropwise to the monomer solution. After the addition was complete, 200 grams of PGME was added to the reaction mixture. The stirring was continued at room temperature for 16 hours. Then, the IPA and water were evaporated to obtain a 2% solid solution. The reaction product was finally obtained after filtering through a 0.2 micron filter. The sample preparation process was the same as above, except that the amount of titanium aluminum oxide added was 10 wt%. , as in Example 17.

[0205] Example 19 Polymer 1 + hafnium oxide nanoparticles = 90:10% by weight Hafnium oxide nanoparticle synthesis: Controlled hydration of hafnium(IV) n-butoxide to nanoparticles It was synthesized by decomposition / condensation of 20 grams of hafnium(IV) n-butoxide (95%) with -butanol solvent (800 grams). The molar ratio of hafnium:MAA=1:1.5 methacrylic acid (MAA, 5.26 grams) was added and mixed for 1 hour. A mixture of water (2.91 grams) and n-BuOH (600 grams) was added dropwise to the reaction medium. After the addition was complete, the reaction was continued for 20 hours. The ethanol was evaporated until a 3% solid solution was obtained. The reaction product was a 0.2 micron filtrate. This was achieved after filtering the solution through a filter. Next, the polymer prepared in Example 1 was diluted with PGMEA. The amount of hafnium oxide nanoparticles was adjusted to 1:1 by mass ratio of polymer 1:HfOx The two solutions were mixed at room temperature for 30 minutes. The mixture was filtered through a 0.2 micrometer plastic micron filter.

[0206] Polymer Testing The molecular weights of the polymers of Examples 14 to 18 were measured on GPC. The film samples contained 2% poly Prepare the mer solution by spin-coating at a spinning speed of 1500 rpm for 30 seconds. Next, soft baking was performed at a temperature range of 80° C. to 150° C. for 30 seconds to 2 minutes.

[0207] The GPC data and post-coating retardation data for the materials are shown in Table 4. Table 4. Post-coating delay for materials made with different compositions.

[0208] [Table 4]

[0209] Legend (for PCD results): X=80 o C / 1h and 150 o Good for at least 1h of PCD after firing at C / 1h, Y=80 o Good after C / 1h, but not good at 150C / 1h. Z=80 o C / 1h and 150 o Both C / 1h are defective. Note: For EUVL, the PCD time must be at least 1 hour for a safe exposure.

[0210] Evaluation of the results. Examples 14-19 show the beneficial effect of the added metal oxide material. The addition of a small weight percent of metal oxide material can substantially reduce the required dose. can be done.

[0211] FIG. 9 shows the e-beam results for a) Example 1, b) Example 14, and c) Example 17. The dose required to obtain a turn decreased by b) 17%, and c) 33%.

[0212] Example 20 Polymer 1 + Photoacid The polymer of Example 1 was diluted with PGMEA to obtain a solution with a solids content of 2%. Iodonium, (4-methylphenyl)[4-(2-methylpropyl)phenyl]-, heptyl The photoacid was dissolved in the polymer solution. A magnetic stirrer was used for dispersion.

[0213] The polymer containing the photobase showed a slight enhancement compared to that of the polymer without the photoacid. E-beam sensitivity was demonstrated. Example 21 Polymer 1 + Photobase The polymer of Example 1 was diluted with PGMEA to give a solution with a solids content of 2%. [Bis(dimethylamino)methylidene]amino}-N-cyclohexyl(cyclohexyl Amino)-methaniminium tetrakis(3-fluorophenyl)borate 5% by weight and 2% by weight of 2-isopropylthioxanthone as a sensitizer was added to the polymer solution. Added.

[0214] The polymer containing the photobase showed a slight increase in the photosensitivity compared to that of the polymer without the photobase and sensitizer. The results show slightly enhanced e-beam sensitivity.

[0215] Evaluation of the results: Examples 20 and 21 show that the materials are resin compositions with similar performance to Example 1. This demonstrates that photoacid and photobase generators can be combined in a common photoacid and photobase generator to obtain the desired composition (Figure 1). 0).

[0216] Abbreviation CAR: Chemically Amplified Resist EBL: Electron Beam Lithography EUV: Extreme ultraviolet light (wavelength) EUVL: Extreme Ultraviolet Lithography GPC: Gel Permeation Chromatography HSQ: Hydrogen silsesquioxane LER: Line edge roughness LWR: Line width roughness NIL: Nanoimprint Lithography PBL: Photon beam lithography PCD: Post-coating delay SEM: Scanning electron microscope TEOS: Tetraethoxysilane TMAH: Tetramethylammonium hydroxide References Non-Patent Literature 1. Okoroanyanwu, U. Molecular Theory of Lithography. (SPIE Press, 2015). 2. Gangnaik, A. S., Georgiev, Y. M. & Holmes, J. D. New Generation Electron Beam Resists: A Review. Chem. Mater. 29, 1898‐1917 (2017). 3.Simone, D. De et al. Progresses and Challenges of EUV Lithography Materials. J . Photopolym. Sci. Technol. 27, 601‐610 (2014). 4. Higgins, C. D. et al. Resolution, line‐edge roughness, sensitivity tradeoff, and quantum yield of high photo acid generator resists for extreme ultraviolet lithography. Jpn. J. Appl. Phys. 50, 1‐8 (2011). 5. De Simone, D., Vesters, Y. & Vandenberghe, G. Photoresists in extreme ultravi olet lithography (EUVL). Adv. Opt. Technol. 6, 163‐172 (2017). 6. Takeo Watanabe. Current status and prospect for EUV lithography. 2017 7th Int . Conf. Integr. Circuit, Des. Verif. 3‐8 (2017). 7. Grigorescu, A. E. & Hagen, C. W. Resists for sub‐20‐nm electron beam lithog raphy with a focus on HSQ: State of the art. Nanotechnology 20, 292001 (2009). 8. Yang, J. K. W. et al. Understanding of hydrogen silsesquioxane electron resis t for sub‐5‐nm‐half‐pitch lithography. J. Vac. Sci. Technol. B Microelectron . Nanom. Struct. 27, 2622 (2009).

Claims

1. A resin exhibiting a silicon-oxygen network, silanol (Si-OH), silicon-hydrogen (Si-H), and optionally silicon-carbon bonds, or A silicon-oxygen-metal network, a resin exhibiting silanol (Si-OH), silicon-hydrogen (Si-H), and optionally silicon-carbon bonds. A hydrogen silsesquioxane resin coating composition for use as a photoresist, comprising in the liquid phase, A hydrogen silsesquioxane resin coating composition in which the ratio of Si-H to Si-OH peak heights in the FTIR spectrum is approximately 2:1 to 100:

1.

2. The composition according to claim 1, having a silicon content of approximately 35% by weight or more.

3. The composition according to claim 1 or 2, wherein the hydrogen silsesquioxane resin has a Si-H to Si-OH peak height ratio of 3:1 to 50:

1.

4. A composition according to any one of claims 1 to 3, comprising an organosiloxane polymer in a solvent that is at least partially crosslinked and optionally contains a metal, wherein the polymer has a molecular weight of about 500 to 100,000 g / mol, particularly about 1,000 to 50,000 g / mol, as measured against a polystyrene standard.

5. A composition according to any one of claims 1 to 4, comprising an acid or a latent acid or a base or a latent base, and optionally a latent catalyst.

6. The composition according to any one of claims 1 to 5, wherein the liquid phase is optionally mixed with water by at least one organic solvent for the hydrogen silsesquioxane resin.

7. A composition according to any one of claims 1 to 6, comprising a metal selected from the group consisting of zirconium, hafnium, aluminum, titanium, and tin, and combinations thereof.

8. The composition according to any one of claims 1 to 7, comprising a silanol-containing polyhydridosilsesquioxane resin solution obtained by hydrolyzing / condensing a trifunctional silane with a suitable other silicon or metal-containing precursor, thereby producing a metal and silanol-containing polyhydridosilsesquioxane.

9. The polymer comprises a siloxane polymer containing an SiO moiety, a plurality of reaction sites distributed along the polymer, a first SiH moiety, a second SiOH moiety, intermediate aromatic and non-aromatic moieties, and a fourth moiety containing a metal-oxygen bond, wherein the polymer has a molecular weight of 500 to 50,000 g / mol. Preferably, the composition according to any one of claims 1 to 8 further comprises an acid and / or base catalyst and a solvent.

10. Equation (I): 【Chemistry 1】 A composition according to any one of claims 1 to 9, comprising a polyhydride silsesquioxane resin having, During the ceremony, A, B, C, and D each represent an integer independently selected from 1 to 1000. Z represents a functional group. M represents a metal atom. R 1 ~R 8 This represents a hydrocarbyl radical, a, b, m, o, y, z, p, q, and x each independently represent an integer between 0 and 3. composition.

11. It is suitable for use in patterning by irradiation. In particular, it is suitable for the production of coating formulations that can be cast onto a substrate. The composition according to any one of claims 1 to 10, wherein the coating on the substrate is patternable by irradiation.

12. A method for producing a composition for use as a photoresist, comprising hydrolyzing / condensing a trifunctional silane with another silicon or metal-containing precursor to obtain a metal and silanol-containing polyhydridosilsesquioxane resin in an organic solution, wherein the composition contains a metal and silanol-containing polyhydridosilsesquioxane resin.

13. A first monomeric hydrogen-containing silicon compound, in which at least two or three hydrolyzable groups are bonded to silicon, 1) A second monomeric silicon compound having at least zero, one, two, or three hydrocarbyl radicals and at least one hydrolyzable group bonded to a silicon atom of the compound, at will 2) A third monomeric silicon compound having at least one functional group and at least one hydrolyzable group that bond to the silicon atom of the compound to form a siloxane material, wherein the functional group enhances solubility in a developer, 3) A fourth compound containing one or more hydrolyzable metal oxide precursors, Hydrolysis together with at least one of the following, The siloxane material is incorporated into a stable composition in a suitable solvent system. The method according to claim 12, including the method described in claim 12.

14. The method according to claim 12 or 13, wherein the first and second silicon compounds are used in an amount of 0 to 100 mol%, the third silicon compound in an amount of 0 to 20 mol%, and the fourth metal compound in an amount of 0 to 50 mol%, and the total amount of the first and second silicon compounds is at least 50 mol%, particularly at least 60 mol%, for example at least 70 mol%.

15. The above formula II: R 1 a ‐Si‐R 2 b ・・・(II) A method according to any one of claims 12 to 14, comprising hydrolyzing a first silicon compound having, During the ceremony, a is an integer of 1 or 2. b is an integer of 2 or 3, R 1 This represents a hydrogen atom. R 2 A method in which a hydrolyzable group can be independently selected from hydroxyl groups, alkoxys, acyloxys, and halogens.

16. the symbols a, b, R 1 and R 2 a first silicon compound having the formula II, in which a, b, and R are the same as described above, Formula III: R 3 m ‐SiR 2 n ‐R 4 o ・・・(III) Together with a second compound having, This includes producing a copolymer (organosiloxane) by hydrolysis. A method according to any one of claims 12 to 15, During the ceremony, R 3 and R 4 This is independently selected from alkyl groups, aryl groups, aralkyl groups, halogenated alkyl groups, halogenated aryl groups, halogenated aralkyl groups, organic groups having epoxy groups, mercapto groups, alkoxyaryl groups, acyloxyaryl groups, isocyanurate groups, hydroxyl groups, cyclic amino groups, or cyano groups, or R 2 and R 3 represents an alkoxy group, an acyloxy group, or a halogen group. m is an integer between 0 and 1. n is an integer between 2 and 4. o is an integer between 0 and 1. The sum of m + n + o does not exceed 4.

17. The aforementioned symbols a, b, R 1 and R 2 A first silicon compound having the formula II, wherein the same as above, Formula IV: Z x ‐R 5 y ‐SiR 2 n ‐R 6 z ・・・(IV) Together with a second compound having, A method according to any one of claims 12 to 16, comprising producing a composition containing a copoli (organosiloxane) by hydrolysis, During the ceremony, Z is a group selected from hydroxy, carboxylic acids, mercaptos, amines or their salts, or quaternary ammonium salts that promote solubility in aqueous developers. R 5 This is a spacer group covalently bonded to both Z and Si, and can be independently selected from divalent groups derived from alkyl groups, aryl groups, aralkyl groups, alkyl halides, aryl halides, aralkyl halides, alkoxyaryl groups, acyloxyaryl groups, or combinations thereof. R 6 This is independently selected from alkyl groups, aryl groups, aralkyl groups, halogenated alkyl groups, halogenated aryl groups, halogenated aralkyl groups, organic groups having epoxy groups, mercapto groups, alkoxyaryl groups, acyloxyaryl groups, hydroxyl groups, cyclic amino groups, or cyano groups, or combinations thereof. R 2 These are alkoxy groups, acyloxy groups, or halogen groups. y is an integer between 0 and 2. n is an integer between 1 and 3. z is an integer between 0 and 11. The method for ensuring that the sum of y + n + z is 4 or less.

18. The aforementioned symbols a, b, R 1 and R 2 A first silicon compound having the formula II, wherein the same as above, Formula V: R 7 p ‐ MR 8 q ・・・(V) Together with a second compound having, A method according to any one of claims 12 to 17, comprising producing a copolymer (organosiloxane) by hydrolysis, During the ceremony, R 7 This is independently selected from alkyl groups, aryl groups, aralkyl groups, halogenated alkyl groups, halogenated aryl groups, halogenated aralkyl groups, alkenyl groups, alkoxyaryl groups, acyloxyaryl groups, or combinations thereof. M is independently selected from metals capable of forming precursors that can be hydrolyzed and condensed into metal oxides or metal-oxohydroxides. p is an integer between 0 and 1. M is capable of forming a stable carbon-metal bond. q is M ox - An integer number obtained from p, M ox This is the oxidation state of the metal precursor, p is a carbon radical R that covalently bonds to a metal precursor. 7 It is the number of, R 8 is an oxygen atom that functions as a bond with an alkoxy group, acyloxy group, halogen group, hydroxide group or other metal atom, or R 8 A method that involves a binary or coordinating ligand of a metal.

19. HTEOS (HSi(OC 2 H 5 ) 3 The method according to any one of claims 12 to 18, comprising using a mixture of ) or HTEOS and other trifunctional silanes, and undergoing a controlled hydrolysis / condensation reaction to produce a partially condensed polyhydride silsesquioxane resin.

20. The method according to claim 19, wherein the trifunctional silane is typically selected from methyltrimethoxysilane (MTMOS), methyltriethoxysilane (MTEOS), trimethoxyethylsilane (ETMOS), diethoxydimethylsilane (DMDEOS), or trimethoxyphenylsilane (PhTMOS), or a combination thereof.

21. A method for patterning a metal and silanol-containing polyhydride silsesquioxane coated substrate by emitting light of a specific wavelength, The substrate is coated with the hydrogen silsesquioxane resin coating composition for use as a photoresist according to claim 1. The coated substrate is irradiated along a selected pattern to form an irradiated structure having irradiated coated areas and unirradiated coated areas. The irradiated structure is selectively developed to remove a significant portion of the unirradiated coating and form a patterned substrate. Methods that include...

22. The method according to claim 21, wherein a metal and silanol-containing polyhydride silsesquioxane coated substrate is irradiated with light of radiation having a wavelength of 1 to 200 nm.

23. The method according to claim 22, wherein a metal and silanol-containing polyhydride silsesquioxane coated substrate is irradiated with light of radiation having a wavelength of 13.5 nm.

24. The method according to any one of claims 21 to 23, wherein the coating comprises a siloxane polymer containing an SiO moiety, a plurality of reaction sites distributed along the polymer, and a first SiH moiety, a second SiOH moiety, and aromatic and non-aromatic intermediate moieties, and a fourth moiety containing a metal-oxygen bond, and the polymer has a molecular weight of 500 to 50,000 g / mol.

25. The aforementioned coating is based on formula (I): 【Chemistry 2】 A method according to any one of claims 21 to 24, comprising a polyhydride silsesquioxane resin having, During the ceremony, A, B, C, and D each represent an integer independently selected from 1 to 1000. Z represents a functional group. M represents a metal atom. R 1 ~R 8 This represents a hydrocarbyl radical, a, b, m, o, y, z, p, q, and x each independently represent integers from 0 to 3.

26. A method according to any one of claims 21 to 25, comprising patterning a substrate, The coated substrate is irradiated along a selected pattern to form an irradiated structure in the irradiated and unirradiated coated regions, the coated substrate includes a coating having an average thickness of about 5 nm to about 400 nm, and includes a Si-O-Si network having Si-H and Si-OH bonds in its material structure, The irradiated structure is heated at a temperature of approximately 45°C to approximately 200°C for 0.1 minutes to approximately 30 minutes to form an annealed irradiated structure. To remove a significant portion of the un-irradiated coating, the annealed and irradiated structure is selectively developed to form a patterned substrate, Methods that include...

27. The method according to any one of claims 21 to 26, wherein the irradiated structure has an irradiated coating that is insoluble in an aqueous base and a non-irradiated coating that is water-soluble in an aqueous base, and the irradiated structure is subjected to negative tone imaging.

28. The method according to any one of claims 21 to 27, comprising patterning a substrate having a surface and a coating present in selected regions along the surface but absent in other regions along the surface, wherein the coating comprises a silicon-oxygen or silicon-oxygen-metal network having silicon-carbon bonds and silicon-hydrogen and / or silanol bonds, and the coating is soluble in an organic liquid or an aqueous base.

29. A method for forming a resist film by applying a resist underlayer formation composition according to any one of claims 1 to 11 onto a semiconductor substrate and firing it.

30. The process involves applying a resist underlayer or several underlayers onto a semiconductor substrate, firing the composition to form one or more resist underlayers, A resist film is formed by applying the composition according to any one of claims 1 to 11 as a resist onto one or more resist underlayer films, Exposing the resist film to light, After exposure, the resist film is developed to form a resist pattern, Etching the resist underlayer using the resist pattern, A semiconductor substrate is fabricated using the resist film patterned in this manner and the resist underlayer film patterned in this manner. A method for manufacturing semiconductor devices, including [the specified element].

31. A method for manufacturing a semiconductor device, Forming an organic underlayer on a semiconductor substrate, The method involves applying the composition according to any one of claims 1 to 11 to form a resist film on the organic undercoat, and then firing it to form a resist film. Exposing the resist film to light, After exposure, the resist film is developed to form a resist pattern, Etching the resist underlayer using the aforementioned resist pattern, Etching the organic underlayer using the resist underlayer patterned in this manner, A semiconductor substrate is fabricated using the organic underlayer film patterned in this manner, Methods that include...

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