Liquid crystal SAMs via spin-coating assembly and their area-selective deposition properties

Abstract

A patterned liquid crystal monolayer structure (100) on a patterned substrate (900) is disclosed, the patterned substrate comprising surface regions (500) to which a liquid crystal compound (300) has been grafted as a self-assembled monolayer (SAM) (200) and surface regions (400) on the patterned substrate to which the SAM is not grafted. Also disclosed are compositions of selected liquid crystals (200) with various types of polar anchor groups in organic spin-casting solvents, and methods of using the compositions to selectively deposit SAMs on substrates containing both metallic and non-metallic inorganic silicon compound surface regions, depending on the nature of the polar anchor groups of the liquid crystal compound, on either of these regions, and methods of using the selective SAM deposition as a barrier to selectively deposit a dielectric metal oxide by ALD on the regions to which the SAM is not grafted. JPEG2026500467000066.jpg91165

Description

[Technical Field]

[0001] The disclosed and claimed invention relates to templates on IC substrates formed by liquid crystal self-assembled monolayers (SAMs) with polar anchoring groups that selectively form SAMs only on certain regions of the IC substrate, compositions used to form these templates, methods of forming these templates, and methods of using the selective SAMs as barriers to effect selective ALD deposition of dielectric metal oxides on regions of the IC substrate not protected by the SAM. [Background technology]

[0002] In recent decades, much effort has been made to further improve the miniaturization, cost, speed, power consumption, and versatility of silicon-based integrated circuit (IC) technologies. Significant progress has been made to increase the number of transistors per CPU, with current microprocessors containing up to 4 billion transistors per small unit area. Building these types of processors involves a series of process steps, including photolithography, etching, and deposition. Photolithography is a key step in transistor and resistor fabrication. The primary factor affecting the resolution of the resulting structures is the wavelength of illumination used during photolithography. The shorter the wavelength, the higher the possible resolution and the smaller the pitch size. Currently, 193 nm is the smallest illumination wavelength that has been implemented in ICs, which can provide a pitch of approximately 80 nm; however, the current industry target is to achieve pitch sizes in the single-digit nanometer range for the same unit area.

[0003] To avoid investment in new equipment and materials, multiple patterning photolithography techniques have been introduced to achieve pitches of approximately 40 nm, but multiple patterning comes at the expense of increased number of steps, defects, cost, process time, tools, fab space, consumable materials, and manpower.

[0004] Conventional lithography approaches can use ultraviolet (UV) radiation to expose a photoresist coated on a substrate or layer of substrate through a mask. Positive- or negative-tone photoresists are useful, and they can also contain refractory elements such as silicon to enable dry development using conventional integrated circuit (IC) plasma processing techniques. In positive-tone photoresists, UV radiation passing through the mask causes a photochemical reaction in the photoresist, rendering the exposed areas removable with a developer solution or conventional IC plasma processing. Conversely, in negative-tone photoresists, UV radiation passing through the mask renders the exposed areas less removable with a developer solution or conventional IC plasma processing. Integrated circuit features, such as gates, vias, or interconnects, are then etched into the substrate or layer of substrate, and the remaining photoresist is removed. Using conventional lithography exposure processes, there are limitations to the feature size of integrated circuit features. Further reduction in pattern size is difficult to achieve with radiation exposure due to limitations related to aberrations, focus, proximity effects, the minimum achievable exposure wavelength, and the maximum achievable numerical aperture. Directed self-assembly is one promising approach that has attracted interest in overcoming some of the drawbacks of conventional lithography outlined above. Directed self-assembly of block copolymers is a useful method for generating ever smaller patterned features for the fabrication of microelectronic devices, achieving feature critical dimensions (CD) on the nanoscale. Directed self-assembly methods are desirable for extending the resolution capabilities of microlithography techniques. The need for large-scale integration has led to a continuous reduction in device circuit dimensions and features. In the past, the ultimate resolution of features has depended on the wavelength of light used to expose the photoresist, which has its own limitations. A recent technology for achieving desired pitches using shorter wavelength light is extreme ultraviolet lithography (EUV), which theoretically could achieve a maximum pitch resolution of approximately 13.5 nm. However, this technique has a high defect rate, which is not in line with industrial expectations.EUV-specific defects are generalized as mask defects, which are a combination of substrate, multilayer blank, and absorber patterning defects. Additionally, this technology is particularly costly, with only 53 production-capable machines in the world. Guided assembly techniques, such as graphoepitaxy and chemoepitaxy using block copolymer imaging, are highly desirable techniques used to enhance resolution while reducing CD variation. These techniques can be used to enhance conventional UV lithography techniques or to enable even higher resolution and CD control in approaches using EUV, e-beam, deep UV, or immersion lithography.

[0005] Directed self-assembly (DSA) of block copolymer (BCP) lithography is an additional alternative or complementary method to conventional lithography, differing from the above methods in that it involves a combination of bottom-up and top-down techniques. A template formed using photolithography / EUV technology (top-down method) is spin-coated with BCP, which is then phase-separated with very high resolution (single-digit nanometer order) under the influence of a guide pattern (template) (bottom-up method). One block is then selectively etched to obtain the desired pitch pattern, depending on the size of the block.

[0006] In IC technology, area-selective deposition of organic or inorganic materials is one of the key processes in the IC industry, requiring exclusive selectivity to either metals or dielectrics via direct or indirect assembly processes. One such application is the passivation of dielectric or metal surfaces on a given patterned substrate for area-selective deposition of metal oxides by atomic layer deposition (ALD). This application requires the selective grafting of organic materials, such as self-assembled monolayers (SAMs) or chain-end functionalized polymers (brushes), to introduce subsequent deposition or assembly processes that enable passivation of the underlying selective regions. A simple method, such as spin-coating organic materials, that can exhibit selectivity to specific regions of a substrate during chip fabrication lithography processes is highly sought after in the industry for ALD or DSA. Common methods for SAM deposition are solution or immersion deposition and vapor phase deposition. Both of these methods have their own advantages and disadvantages. The chemistry and processing of SAM precursors limit their selective deposition via spin-coating.

[0007] In liquid crystal display (LCD) technology, alignment of liquid crystals (LCs) on glass or indium tin oxide (ITO) surfaces is achieved by surface modification to enable alignment of LCs. This is achieved by surface modification with alkylsilanes, with or without IC components and siloxy functional groups. In this approach, the glass or ITO surface is modified with alkoxysilane SAMs using solution dip coating and vapor-phase delivery. Liquid crystal compounds (LCCs) with functional groups such as carboxylic acid, hydroxyl, amine, and thiol are known and are used in liquid crystal display (LCD) technology as pure materials or as mixtures with photocurable polymer matrices.

[0008] Atomic layer deposition (ALD) is an important technique for depositing thin films for various applications in the semiconductor field. It is advantageous because it provides precise thickness control at the angstrom or monolayer level due to its self-limiting surface chemistry. Due to the increasing demands of semiconductor roadmaps that test the limits of previous electronic materials, ALD is becoming increasingly important because it can control deposition at the atomic scale and conformally deposit on very high aspect ratio structures. For the fabrication of 3D devices, lateral patterning of ALD is used, for example, by using conventional photoresists and photolithography (e.g., semiconductor processing), other masking polymer layers, direct-write electron beam technology that selectively removes masking layers to enable ALD in those areas, or by using patterned octadecyltrichlorosilane monolayers.

[0009] A need exists for a simple method that is compatible with standard IC track equipment and spin-coatable, that can easily form self-assembled monolayers (SAMs) while providing high densities of moieties that can selectively protect metal or non-metal surface areas on IC substrates to enhance atomic layer deposition of dielectric metal oxides in the unprotected areas, and that is compatible with modern methods of IC patterning, such as nanometer-sized dimensions based on EUV, DSA, and combinations of these techniques. [Brief explanation of the drawings]

[0010] [Figure 1] FIG. 1 is a schematic diagram of a spin-on SAM assembly of liquid crystal molecules. [Figure 2] FIG. 2 is a schematic drawing of a portion of a cross section perpendicular to a patterned substrate, only a portion of which has a liquid crystal top SAM composed of a linear alkyl group, a central core with at least two phenyl moieties, and a polar anchor group. [Figure 3] FIG. 3 is a schematic drawing of a liquid crystal compound (300). [Figure 4]Figure 4 shows the thermal stability of the SAMs via the change in water contact angle (SAMs were heated at different temperatures under nitrogen for 5 minutes). [Figure 5] FIG. 5 shows the SAM thermal stability via changes in XPS carbon atom percentage (SAMs were heated at different temperatures under nitrogen for 5 minutes). [Figure 6] FIG. 6 shows the passivation properties of a dielectric SAM upon atomic layer deposition of hafnium oxide at 300° C. [Figure 7] FIG. 7 shows the characterization of SAM selectivity using XPS. [Figure 8] FIG. 8 shows the passivation properties for ALD of HfOx at 200° C. [Figure 9] FIG. 9 shows the passivation properties for ALD of HfOx at 200° C. [Prior art documents] [Patent documents]

[0011] [Patent Document 1] JP2017025007 [Patent Document 2] WO2014 / 094959A1 [Patent Document 3] WO2017045740 [Patent Document 4] EP2883934 [Patent Document 5] US8741176B2 [Non-patent literature]

[0012] [Non-Patent Document 1] Kanie,Kiyoshi et al.,Chemistry Letters 1995,24,68 Summary of the Invention

[0013] This disclosure describes a spin-coatable composition comprising a liquid crystal having an anchoring group and an organic spin-coating solvent, which, when spin-coated onto an IC substrate containing metallic and non-metallic inorganic silicon compound surface regions, selectively forms self-assembled monolayers (SAMs) on some of these regions, modifying the properties of these regions. Examples of non-metallic inorganic silicon regions are silicon oxide (SiO), silicon nitride (SiN), and silicon oxynitride, while examples of metallic regions are copper and tungsten. Selective SAM monolayer formation on either of these surface region substrate types depends on the anchoring group, and can be achieved by spin-coating and baking compounds (LCCs) with different anchoring groups and then rinsing the film with a processing solution (Figure 1). This type of selective surface property enhancement enables selective passivation for atomic layer deposition of dielectric metal oxides such as titanium oxide, aluminum oxide, hafnium oxide, and the like.

[0014] More specifically, the present invention provides a template that is a patterned liquid crystal monolayer structure (100) on a patterned substrate (900), comprising: a patterned substrate (900) comprising a first surface region (500) having a liquid crystal compound (300) adsorbed thereon as a self-assembled monolayer (SAM) (200) and a second surface region (400) free of the liquid crystal compound (300); provided that: The liquid crystal compound (300) comprises a cylindrical linear organic liquid crystal core structure, the cylindrical linear organic liquid crystal core structure comprising at least one 1,4-phenylene moiety (700), the at least one 1,4-phenylene moiety (700) having attached to one end thereof a linear alkyl group (600) containing at least two carbon atoms, and attached to the other end thereof a polar anchor group (800) selected from the group consisting of a phosphonate ester-containing moiety, a phosphonic acid-containing moiety, a thiol-containing moiety, an amino-containing moiety, a moiety containing at least one alkylene hydroxyl, and an alkyl-polyol-containing moiety; In the self-assembled monolayer (200), the liquid crystal compounds (300) are aligned in the self-assembled monolayer (200) such that each liquid crystal compound in the self-assembled monolayer (200) is parallel to each other and oriented in the same direction, perpendicular to the patterned substrate (900) and bound to the surface region (500) only via the polar anchor groups (800); and Any of the following: - if the polar anchor group (800) is either an alkyl-polyol coordinating moiety or a moiety containing at least one alkylene hydroxy, the surface region (500) to which the self-assembled monolayer (200) is attached is a non-metallic inorganic silicon compound-based surface region, and the surface region (400) without the liquid crystal compound (300) is a metallic surface region, or - if the polar anchor group is selected from the group consisting of phosphonate-containing moieties, phosphonic acid-containing moieties, thiol-containing moieties, and amino-containing moieties, the surface region (500) to which the self-assembled monolayer (200) is attached is a metallic surface region, and the surface region (400) without the liquid crystal compound (300) is a non-metallic inorganic silicon compound-based surface region, Either Regarding the template.

[0015] 2 shows a schematic drawing of a portion of a cross section taken perpendicular to the template, along with a caption describing the portion of the template. The template on a substrate consists of a protective SAM of liquid crystal selectively formed only in certain areas of the substrate to promote atomic layer deposition (ALD) of a dielectric metal oxide in areas not covered by the SAM.

[0016] The present invention also relates to a composition comprising a liquid crystalline compound (300) and an organic spin-casting solvent, wherein the liquid crystalline compound comprises a cylindrical linear organic liquid crystalline core structure, the cylindrical linear organic liquid crystalline core structure comprising at least one 1,4-phenylene moiety (700), which has attached to one end a linear alkyl group (600) having at least two carbon atoms and attached to the other end a polar anchor group (800). Figure 3 shows a schematic drawing of the liquid crystalline compound (300).

[0017] The present invention also relates to a method for preparing the above template and to a method for using this template to effect selective ALD of a dielectric metal oxide on areas of the template that are not protected by the liquid crystal SAM (300). Another aspect of the present invention is the use of a composition according to any one of claims 10 to 27 or of a liquid crystal compound (300) as defined in any one of claims 1 to 9 for the selective formation of a self-assembled monolayer on either the metallic or non-metallic areas of a hybrid substrate containing both metallic and non-metallic areas. DETAILED DESCRIPTION OF THE INVENTION

[0018] It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive with respect to the invention as claimed. As used herein, unless specifically stated otherwise, the use of the singular includes the plural, the singular means "at least one," and the use of "or" means "and / or." Furthermore, the use of "comprises" and other verb forms, such as "comprises," is not limiting. Furthermore, references to "elements" or "components" include both elements and components containing one unit and elements or components containing more than one unit, unless specifically stated otherwise. Unless otherwise indicated, the conjunction "and" as used herein is intended to be inclusive, and the conjunction "or" is not intended to be exclusive. For example, the phrase "or instead" is intended to be exclusive. As used herein, the conjunction "and" refers to any combination of the aforementioned elements, including the use of a single element.

[0019] The section headings used herein are for organizational purposes only and should not be construed as limiting the inventions described. All references or portions thereof cited herein, including but not limited to patents, patent applications, papers, books, and treatises, are hereby incorporated by reference in their entirety for all purposes. In the event that the definition of a term in one or more of the references and similar materials cited herein conflicts with that herein, the definition herein shall control.

[0020] Unless otherwise indicated, "alkyl" refers to a hydrocarbon group, which can be linear or branched (e.g., methyl, ethyl, propyl, isopropyl, tert-butyl, and the like), cyclic (e.g., cyclohexyl, cyclopropyl, cyclopentyl, and the like), or polycyclic (e.g., norbornyl, adamantyl, and the like). These alkyl moieties can be substituted or unsubstituted as described below. The term "alkyl" refers to such moieties having C1 to C8 carbons. For structural reasons, it is understood that linear alkyls begin at C1, while branched and cyclic alkyls begin at C3, and polycyclic alkyls begin at C5. Furthermore, moieties derived from alkyls described below, such as alkyloxy (alkoxy), are understood to have the same carbon number range unless otherwise specified. This same rule applies to the description of C1 to C4 alkyl. Where a different alkyl group length than those above is specified, the above definition of alkyl remains valid in that it encompasses all types of alkyl moieties above, and the structural considerations above regarding the minimum carbon number of a given type of alkyl group still apply.

[0021] Alkyloxy (also known as alkoxy) refers to an alkyl group attached through an oxy (-O-) moiety (e.g., methoxy, ethoxy, propoxy, butoxy, 1,2-isopropoxy, cyclopentyloxy, cyclohexyloxy, and the like). These alkyloxy moieties may be substituted or unsubstituted as described below. The criteria for establishing the type of alkyl in a C1-C8 alkoxy or C1-C4 alkoxy are the same as those described above for the alkyl moiety.

[0022] Halo or halide refers to a halogen, F, Cl, Br, or I, attached to an organic moiety by one bond.

[0023] Haloalkyl refers to a linear, cyclic, or branched saturated alkyl group, as defined above, in which at least one of the hydrogens has been replaced by a halide selected from F, Cl, Br, I, or mixtures thereof, if more than one halo moiety is present. Fluoroalkyl is a specific subgroup of these moieties.

[0024] The term "alkylene," unless otherwise indicated, refers to a hydrocarbon group that can be linear, branched, or cyclic, having two or more points of attachment (e.g., methylene, ethylene, 1,2-isopropylene, 1,4-cyclohexylene, and the like, having two points of attachment; 1,1,1-substituted methanes, 1,1,2-substituted ethanes, 1,2,4-substituted cyclohexanes, and the like, having three points of attachment). Again, when specifying a range of possible carbon numbers, such as, as a non-limiting example, C1 to C20, this range includes linear alkylene beginning at C1, but specifies only branched alkylene or cycloalkylene beginning at C3. These alkylene moieties can be substituted or unsubstituted, as described below. The term linear alkylene, unless otherwise indicated, refers to a linear alkylene moiety having two points of attachment that is unsubstituted.

[0025] The term "acyl" refers to a (-C=O)-R moiety, where R is H, aryl, or alkyl.

[0026] The term "aryl" or "aromatic group" refers to such groups containing 6 to 24 carbon atoms, such as phenyl, tolyl, xylyl, naphthyl, anthracyl, biphenyls, bis-phenyls, tris-phenyls, and the like. These aryl groups may be further substituted with any suitable substituents, such as alkyl, alkoxy, acyl, or aryl groups as described above.

[0027] Unless otherwise indicated herein, the term "substituted" when referring to aryl, alkyl, alkyloxy, fluoroalkyl, fluoroalkyloxy, fused aromatic ring, arene, heteroarene, includes any one of these moieties, including unsubstituted alkyl, substituted alkyl, unsubstituted aryl, alkyloxyaryl (alkyl-O-aryl-), dialkyloxyaryl ((alkyl-O-)2-aryl), haloaryl, alkyloxy, alkylaryl, haloalkyl, halide, hydroxyl, cyano, nitro, acetyl, alkylcarbonyl, formyl, ethenyl (CH2=CH-), phenylethenyl (Ph-CH=CH-), arylethenyl (aryl-CH=CH), and ethenylenearylene moieties (e.g., Ar(-CH=CH-Ar-)). z (z=1-3) Specific non-limiting examples of substituted aryl and substituted arylethenyl substituents are as follows, where:

[0028] [ka] represents a connection point:

[0029] [ka] The term amino-containing moiety, when used in connection with the polar anchor groups (groups shown schematically as (800) in FIG. 3) of the liquid crystal molecules used in the SAM templates of the present invention (FIG. 2) and liquid crystal compositions of the present invention, refers to an amino group (-NH2) that can be directly attached to the liquid crystal molecule via a covalent bond or via a C1-C8 linear alkylene moiety (-alkylene-NH2) or a C2-C8 linear oxyalkylene moiety (-O-alkylene-NH2).

[0030] The term phosphonate ester-containing moiety, when used in connection with the polar anchor groups (groups shown schematically as (800) in FIG. 3) of liquid crystal molecules used in the SAM templates of the present invention ( FIG. 2 ) and liquid crystal compositions of the present invention, refers to a dialkylphosphonate group (-P(═O)(O-alkyl)2) moiety that can be directly attached to the liquid crystal molecule via a covalent bond or via a C1-C8 linear alkylene moiety (-alkylene-P(═O)(O-alkyl)2) or a C2-C8 linear oxyalkylene moiety (-O-alkylene-P(═O)(O-alkyl)2).

[0031] The term phosphonic acid moiety, when used in connection with the polar anchor groups (groups shown schematically as (800) in FIG. 3) of liquid crystal molecules used in the SAM templates of the present invention (FIG. 2) and liquid crystal compositions of the present invention, refers to a phosphonic acid group (-P(=O)(OH)2) moiety that can be directly attached to the liquid crystal molecule via a covalent bond or via a C1-C8 linear alkylene moiety (-alkylene-P(=O)(OH)2) or a C1-C8 linear oxyalkylene moiety (-O-alkylene-P(=O)(OH)2).

[0032] The term thiol-containing moiety, when used in connection with the polar anchor groups (groups shown schematically as (800) in FIG. 3) of liquid crystal molecules used in the SAM templates of the present invention (FIG. 2) and liquid crystal compositions of the present invention, refers to a thiol group (-SH) moiety that is attached to the liquid crystal molecule via a C1-C8 linear alkylene moiety (-alkylene-SH) or a C2-C8 linear oxyalkylene moiety (-O-alkylene-SH).

[0033] The term alkylene hydroxy-containing moiety, when used in connection with the polar anchor groups (groups shown schematically as (800) in Figure 3) of liquid crystal molecules used in the SAM templates and liquid crystal compositions of the present invention, refers to a hydroxy group (-OH) moiety that is attached to the liquid crystal molecule via a C1-C8 linear oxyalkylene moiety (-O-alkylene-OH) or a C1-C8 linear alkylene moiety (-alkylene-OH).

[0034] The term alkyl-polyol-containing moiety, when used in connection with the polar anchor group (schematically shown as (800) in FIG. 3) of the liquid crystal molecules used in the SAM templates and liquid crystal compositions of the present invention, refers to a C2-C8 linear alkylene moiety (-alkylene-C(alkylene-OH) n , n is 2 or 3) or C2-C8 linear oxyalkylene moiety (-O-alkylene-C(alkylene-OH) n , n is 2 or 3), alkyl polyol (-C(alkylene-OH) n , n is 2 or 3).

[0035] The term "cylindrical linear organic liquid crystal core structure comprising at least one 1,4-phenylene moiety" (shown generally as (700) in FIG. 3) refers to a core structure that contains at least one 1,4-phenylene moiety, but also includes additional different linear moieties, such as additional 1,4-phenylene moieties, 1,4-cyclohexylene moieties, 1,4-phenylene, linear ethylene moieties, which may be substituted or unsubstituted.

[0036] [ka]

[0037] [ka] wherein these linear moieties are bonded to each other to form a linear arrangement in the liquid crystal molecule, which promotes pi-pi interactions among one or more 1,4-phenylene moieties in different liquid crystal molecules, and wherein the liquid-phase molecules (300) (comprising the linear alkyl group (600), the cylindrical linear organic liquid crystal core structure (700), and the polar anchor group (800)) interact with each other through these pi-pi interactions when they are grafted to specific regions of a patterned substrate via their polar anchor groups (800) (FIG. 2). Non-limiting examples of cylindrical linear organic liquid crystal core structures containing at least one 1,4-phenylene moiety are shown in structures (I) to (VIII) described herein.

[0038] The term "linear alkyl group containing at least two carbon atoms" (schematically shown as (600) in Figure 3) of the liquid crystal molecules used in the SAM templates and liquid crystal compositions of the present invention refers to a linear alkyl (also known as an n-alkyl moiety) that has at least two carbon atoms and is unsubstituted.

[0039] One aspect of the present invention is a template of the present invention which is a patterned liquid crystal monolayer structure (100) on a patterned substrate (900), a patterned substrate (900) comprising a first surface region (500) having a liquid crystal compound (300) adsorbed thereon as a self-assembled monolayer (SAM) (200) and a second surface region (400) free of the liquid crystal compound (300); provided that: The liquid crystal compound (300) comprises a cylindrical linear organic liquid crystal core structure, the cylindrical linear organic liquid crystal core structure comprising at least one 1,4-phenylene moiety (700), the at least one 1,4-phenylene moiety (700) having attached to one end thereof a linear alkyl group (600) containing at least two carbon atoms, and attached to the other end thereof a polar anchor group (800) selected from the group consisting of a phosphonate ester-containing moiety, a phosphonic acid-containing moiety, a thiol-containing moiety, an amino-containing moiety, a moiety containing at least one alkylene hydroxyl, and an alkyl-polyol-containing moiety; In the self-assembled monolayer (200), the liquid crystal compounds (300) are aligned in the self-assembled monolayer (200) such that each liquid crystal compound in the self-assembled monolayer (200) is parallel to each other and oriented in the same direction, perpendicular to the patterned substrate (900) and bound to the surface region (500) only via the polar anchor groups (800); and Any of the following: - if the polar anchor group (800) is an alkyl-polyol coordinating moiety or a moiety containing at least one alkylene hydroxy, the surface region (500) to which the self-assembled monolayer (200) is attached is a non-metallic inorganic silicon compound-based surface region, and the surface region (400) without the liquid crystal compound (300) is a metallic surface region, or - if the polar anchor group is selected from the group consisting of phosphonate ester-containing moieties, phosphonic acid-containing moieties, thiol-containing moieties, and amino-containing moieties, the surface region (500) to which the self-assembled monolayer (200) is attached is a metallic surface region, and the surface region (400) without the liquid crystal compound (300) is a non-metallic inorganic silicon compound-based surface region, Either Regarding the template.

[0040] 2 shows a schematic drawing of a portion of a cross section taken perpendicular to the template, along with a caption describing the portions of the template on a substrate on which a protective SAM of liquid crystal selectively forms in only certain areas, which acts to enhance atomic layer deposition (ALD) of a dielectric metal oxide in areas not covered by the SAM.

[0041] In another aspect of the template of the present invention, it is a template consisting of the previously described elements (100), (200), (300), (400), (500), (600), (700) and (800), but no other elements.

[0042] In another aspect of the templates of the invention, the linear alkyl group (600) is a C2-C5 alkyl. In one aspect of this embodiment, the linear alkyl group is ethyl, in another aspect it is n-propyl, in another aspect it is n-butyl, and in another aspect it is n-pentyl.

[0043] In another aspect of the templates of the invention described herein, the cylindrical linear organic liquid crystal core structure comprises at least two 1,4-phenylene moieties (700) selected from the group consisting of structures (I), (II), (IIa), (III), (IV), (V), (VI), (VII) and (VIII), wherein ** is the point of attachment of the linear alkyl group (600) and * is the point of attachment of the polar anchor group (800), and R1 and R2 are independently selected from H, C1-C2 alkyl and F. In another aspect of this embodiment, the 1,4-phenylene moiety (700) has structure (I), in another aspect it has structure (II), in another aspect it has structure (IIa), in another aspect it has structure (III), in another aspect it has structure (IV), in another aspect it has structure (V), in another aspect it has structure (VI), in another aspect it has structure (VII), and in the final aspect it has structure (VIII).

[0044] [ka] In another aspect of the templates of the invention described herein, the polar graft (also known as anchor) group (800) is selected from the group consisting of Structure (Ip), Structure (Ipa), Structure (IIp), and Structure (IIpa), where L1 and L2 are independently selected from C2-C4 linear alkylene spacers, and *** is the point of attachment of the polar anchor group to the liquid crystal compound. In another aspect of this embodiment, the polar graft group (800) has Structure (Ip), in others it has Structure (Ipa), in others it has Structure (IIp), and in others it has Structure (IIpa). In one aspect of the embodiment having Structure (Ip), L1 is a C2 linear alkylene group, in others it is a C3 linear group, and in others it is a C4 linear alkylene group. In one aspect of the embodiment having structure (Ipa), L1 is a C2 linear alkylene group, in others it is a C3 linear group, and in others it is a C4 linear alkylene group. In one aspect of the embodiment having structure (IIp), L2 is a C2 linear alkylene group, in others it is a C3 linear group, and in others it is a C4 linear alkylene group. In one aspect of the embodiment having structure (IIpa), L2 is a C2 linear alkylene group, in others it is a C3 linear group, and in others it is a C4 linear alkylene group.

[0045] [ka] In another aspect of the templates of the invention described herein, the polar graft group (800) is selected from the group consisting of Structure (IIIp), Structure (IVp), Structure (Vp), Structure (VIp), Structure (VIIp), Structure (VIIIp), and Structure (IXp), wherein L3, L4, L5, L6, and L7 are independently selected from C2-C4 linear alkylene spacers; *** is the point of attachment of the polar anchor group to the liquid crystal compound; and R p1 is C1-C4 alkoxy, and R p2is a C1-C4 alkyl or a C1-C4 alkoxy. In one aspect of this embodiment, the polar graft group has structure (IIIp); in one other aspect of this embodiment, L3 is a C2 linear alkylene; in another, L3 is a C3 linear alkylene; and in another, it is a C4 linear alkylene. In one aspect of this embodiment, the polar graft group has structure (IVp). In one aspect of this embodiment, L4 is a C2 linear alkylene; in another, L4 is a C3 linear alkylene; and in another, it is a C4 linear alkylene. In one aspect of this embodiment, the polar graft group has the structure (Vp), where in one aspect of this embodiment, Rp1 is methoxy, in others, it is ethoxy, in others, it is n-propoxy, and in others, it is n-butoxy; in one aspect of this embodiment, Rp2 is methyl, in others, it is ethyl, in others, it is n-propyl, and in others, it is n-butyl; in another aspect of this embodiment, Rp2 is methoxy, in others, it is ethoxy, in others, it is n-propoxy, and in others, it is n-butoxy. In one aspect of this embodiment, the polar graft group has structure (VIp), where in one aspect of this embodiment, Rp1 is methoxy, in others, it is ethoxy, in others, it is n-propoxy, and in others, it is n-butoxy; in one aspect of this embodiment, Rp2 is methyl, in others, it is ethyl, in others, it is n-propyl, and in others, it is n-butyl; in another aspect of this embodiment, Rp2 is methoxy, in others, it is ethoxy, in others, it is n-propoxy, and in others, it is n-butoxy. In another aspect of this embodiment, the polar graft group has structure (VIIp). In another aspect of this embodiment, the polar graft group has structure (VIIIp), where in one aspect of this embodiment, L6 is a C2 linear alkylene, in another aspect, it is a C3 linear alkylene, and in another aspect, it is a C4 linear alkylene.In another aspect of this embodiment, the polar graft group has the structure (IXp), and in one aspect of this embodiment, L7 is a C2 linear alkylene, in another aspect it is a C3 linear alkylene, and in another aspect it is a C4 linear alkylene.

[0046] [ka] In another aspect of the templates of the invention described herein, the liquid crystal compound (300) is selected from the group consisting of those having structures (M1), (M2), (M3), (M4), (M5), and (M7). In one aspect of this embodiment, the liquid crystal compound (300) has structure (M1), in others it has structure (M2), in others it has structure (M3), in others it has structure (M4), in others it has structure (M5), and in others it has structure (M7).

[0047] [ka] In another aspect of the templates of the invention described herein, the liquid crystal compound (300) is selected from the group consisting of those having structures (M8), (M9), (M10), (M11), (M12), (M13), and (M14). In one aspect of this embodiment, the liquid crystal compound (300) has structure (M8), in others it has structure (M9), in others it has structure (M10), in others it has structure (M11), in others it has structure (M12), in others it has structure (M13), and in others it has structure (M14).

[0048] [ka] In another aspect of the template of the invention described herein, the SAM-coated surface region (500) is a non-metallic inorganic silicon compound-based surface region selected from the group consisting of silicon oxide (SiO2), silicon with a native oxide, silicon nitride (SiN) and silicon oxynitride (SiON), and the bare surface region (400) is a metal selected from the group consisting of tungsten, gold, silver, copper, cobalt, ruthenium, zirconium, titanium and hafnium. In one aspect of this embodiment, the SAM-coated surface region (500) is a non-metallic, inorganic, silicon-based surface region, which is silicon dioxide (SiO2), in others it is silicon (Si) with a native oxide, in others it is silicon nitride (SiN), and in others it is silicon oxynitride (SiON); in these respects, in one aspect the bare surface region (400) is tungsten, in others it is gold, in others it is silver, in others it is copper, in others it is cobalt, in others it is ruthenium, in others it is zirconium, in others it is titanium, and in others it is hafnium.

[0049] In another aspect of the template of the invention described herein, the SAM-coated surface region (500) is a metal selected from the group consisting of tungsten, gold, silver, copper, cobalt, ruthenium, zirconium, titanium, and hafnium, and the bare surface region (400) is a non-metallic inorganic silicide-based surface region selected from the group consisting of silicon oxide (SiO2), silicon with a native oxide, silicon nitride (SiN), and silicon oxynitride (SiON). In one aspect of this embodiment, the SAM-coated surface region (500) is tungsten, in others it is gold, in others it is silver, in others it is copper, in others it is cobalt, in others it is ruthenium, in others it is zirconium, in others it is titanium, and in others it is hafnium; in these respects, in one aspect the bare surface region (400) is silicon dioxide (SiO2), in others it is silicon (Si) with a native oxide, in others it is silicon nitride (SiN), and in others it is silicon oxynitride (SiON).

[0050] Compositions of the Invention Another aspect of the present invention is a composition comprising a liquid crystal compound (300) and an organic spin-casting solvent, wherein the liquid crystal compound comprises a cylindrical linear organic liquid crystal core structure, the cylindrical linear organic liquid crystal core structure comprising at least one 1,4-phenylene moiety (700), which has attached to one end a linear alkyl group (600) having at least two carbon atoms and attached to the other end a polar anchor group (800). In another aspect of this embodiment, the composition comprises a liquid crystal compound (300) and an organic spin-casting solvent.

[0051] In another aspect of the composition, in liquid crystal compound (300), the linear alkyl group (600) is a C2-C5 alkyl. In one aspect of this embodiment, the linear alkyl group is ethyl, in others it is n-propyl, and in others it is n-butyl.

[0052] In another aspect of the composition, in liquid crystal compound (300), the cylindrical linear organic liquid crystal core structure comprising at least two 1,4-phenylene moieties (700) is selected from the group consisting of structures (I), (II), (IIa), (III), (IV), (V), (VI), (VII), and (VIII), where ** is the point of attachment of the linear alkyl group (600) and * is the point of attachment of the polar anchor group (800), and R1 and R2 are independently selected from H, C1-C2 alkyl, and F. In another aspect of this embodiment, the linear organic liquid crystal core structure comprising at least two 1,4-phenylene moieties (700) has structure (I); in one aspect of this embodiment, R1 is H, in others it is methyl, and in others it is F; in one aspect of these embodiments, R2 is H, in others it is methyl, and in others it is F. In another aspect of this embodiment, the linear organic liquid crystal core structure comprising at least two 1,4-phenylene moieties (700) has structure (II); in one aspect of this embodiment, R1 is H, in others it is methyl, and in others it is F; in one aspect of these embodiments, R2 is H, in others it is methyl, and in others it is F. In another aspect of this embodiment, the linear organic liquid crystal core structure comprising at least two 1,4-phenylene moieties (700) has structure (IIa); in one aspect of this embodiment, R1 is H, in others it is methyl, and in others it is F; in one aspect of these embodiments, R2 is H, in others it is methyl, and in others it is F. In another aspect of this embodiment, the linear organic liquid crystal core structure comprising at least two 1,4-phenylene moieties (700) has structure (III); in one aspect of this embodiment, R1 is H, in others it is methyl, and in others it is F; in one aspect of these embodiments, R2 is H, in others it is methyl, and in others it is F.In another aspect of this embodiment, the linear organic liquid crystal core structure comprising at least two 1,4-phenylene moieties (700) has structure (IV); in one aspect of this embodiment, R is H, in another aspect it is methyl, and in another aspect it is F. In another aspect of this embodiment, the linear organic liquid crystal core structure comprising at least two 1,4-phenylene moieties (700) has structure (V). In another aspect of this embodiment, the linear organic liquid crystal core structure comprising at least two 1,4-phenylene moieties (700) has structure (VI). In another aspect of this embodiment, the linear organic liquid crystal core structure comprising at least two 1,4-phenylene moieties (700) has structure (VI). In another aspect of this embodiment, the linear organic liquid crystal core structure comprising at least two 1,4-phenylene moieties (700) has structure (VII). In another aspect of this embodiment, the linear organic liquid crystal core structure comprising at least two 1,4-phenylene moieties (700) has the structure (VIII).

[0053] [ka] In another aspect of the composition, in liquid crystal compound (300), the polar graft group (800) is selected from the group consisting of Structure (Ip), Structure (Ipa), Structure (IIp), and Structure (IIpa), where L1 and L2 are independently selected from C2-C4 linear alkylene spacers, and *** is the point of attachment of the polar anchor group to the liquid crystal compound. In another aspect of this embodiment, the polar graft group (800) has Structure (Ip), in others it has Structure (Ipa), in others it has Structure (IIp), and in others it has Structure (IIpa). In one aspect of the embodiment having Structure (Ip), L1 is a C2 linear alkylene group, in others it is a C3 linear group, and in others it is a C4 linear alkylene group. In one aspect of the embodiment having structure (Ipa), L1 is a C2 linear alkylene group, in others it is a C3 linear group, and in others it is a C4 linear alkylene group. In one aspect of the embodiment having structure (IIp), L2 is a C2 linear alkylene group, in others it is a C3 linear group, and in others it is a C4 linear alkylene group. In one aspect of the embodiment having structure (IIpa), L2 is a C2 linear alkylene group, in others it is a C3 linear group, and in others it is a C4 linear alkylene group.

[0054] [ka] In another aspect of the composition, in liquid crystal compound (300), the polar graft group (800) is selected from the group consisting of Structure (IIIp), Structure (IVp), Structure (Vp), Structure (VIp), Structure (VIIp), Structure (VIIIp), and Structure (IXp), wherein L3, L4, L5, L6, and L7 are independently selected from C2-C4 linear alkylene spacers; *** is the point of attachment of the polar anchor group to the liquid crystal compound; and R p1 is C1-C4 alkoxy, and R p2is a C1-C4 alkyl or a C1-C4 alkoxy. In one aspect of this embodiment, the polar graft group has structure (IIIp); in one other aspect of this embodiment, L3 is a C2 linear alkylene; in another, L3 is a C3 linear alkylene; and in another, it is a C4 linear alkylene. In one aspect of this embodiment, the polar graft group has structure (IVp). In one aspect of this embodiment, L4 is a C2 linear alkylene; in another, L4 is a C3 linear alkylene; and in another, it is a C4 linear alkylene. In one aspect of this embodiment, the polar graft group has the structure (Vp), where in one aspect of this embodiment, Rp1 is methoxy, in others, it is ethoxy, in others, it is n-propoxy, and in others, it is n-butoxy; in one aspect of this embodiment, Rp2 is methyl, in others, it is ethyl, in others, it is n-propyl, and in others, it is n-butyl; in another aspect of this embodiment, Rp2 is methoxy, in others, it is ethoxy, in others, it is n-propoxy, and in others, it is n-butoxy. In one aspect of this embodiment, the polar graft group has structure (VIp), and in another aspect of this embodiment, Rp1 is methoxy, in others, it is ethoxy, in others, it is n-propoxy, and in others, it is n-butoxy; in one aspect of this embodiment, Rp2 is methyl, in others, it is ethyl, in others, it is n-propyl, and in others, it is n-butyl; in another aspect of this embodiment, Rp2 is methoxy, in others, it is ethoxy, in others, it is n-propoxy, and in others, it is n-butoxy. In another aspect of this embodiment, the polar graft group has structure (VIIp). In another aspect of this embodiment, the polar graft group has structure (VIIIp), and in one aspect of this embodiment, L6 is a C2 linear alkylene, in another aspect, it is a C3 linear alkylene, and in another aspect, it is a C4 linear alkylene.In another aspect of this embodiment, the polar graft group has the structure (IXp), and in one aspect of this embodiment, L7 is a C2 linear alkylene, in another aspect it is a C3 linear alkylene, and in another aspect it is a C4 linear alkylene.

[0055] [ka] In another aspect of the composition, the liquid crystal compound (300) is selected from the group consisting of those having structures (M1), (M2), (M3), (M4), (M5), and (M7). In one aspect of this embodiment, it has structure (M1), in others it has structure (M2), in others it has structure (M3), in others it has structure (M4), in others it has structure (M5), and in others it has structure (M7).

[0056] [ka] In another aspect of the composition, the liquid crystal compound (300) is selected from the group consisting of those having structures (M8), (M9), (M10), (M11), (M12), (M13), and (M14). In one aspect of this embodiment, it has structure (M8), in others it has structure (M10), in others it has structure (M11), in others it has structure (M12), in others it has structure (M13), and in others it has structure (M14).

[0057] [ka] In another aspect of the composition, the liquid crystal compound (300) has the structure (M4).

[0058] [ka] In another aspect of the composition, the liquid crystal compound (300) is selected from the group consisting of those having structures (M8), (M9), (M12), (M13), and (M14). In one aspect of this embodiment, it has structure (M8), in another aspect it has structure (M9), in another aspect it has structure (M12), in another aspect it has structure (M13), and in another aspect it has structure (M14).

[0059] [ka] In another aspect of the composition, the liquid crystal compound (300) is selected from the group consisting of those having the structures (M10) and (M11). In one aspect of this embodiment, it has the structure (M10), and in another, it has the structure (M11).

[0060] [ka] In one of the other aspects, the liquid crystal compound is present in the organic spin-coating solvent in an amount of from about 0.5% to about 2.0% by weight.

[0061] In another aspect of the composition, the organic spin-coating solvent is a single organic solvent or a mixture of at least two organic solvents, the organic spin-coating solvent being a glycol ether derivative selected from ethyl cellosolve, methyl cellosolve, propylene glycol monomethyl ether (PGME), diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, dipropylene glycol dimethyl ether, propylene glycol n-propyl ether, or diethylene glycol dimethyl ether; a glycol ether ester derivative, such as ethyl cellosolve acetate, methyl cellosolve acetate, or propylene glycol monomethyl ether acetate (PGMEA); a carboxylate of a monobasic acid selected from ethyl acetate, n-butyl acetate, and amyl acetate; a carboxylate of a dibasic acid selected from diethyl oxylate and diethyl malonate; a carboxylate of a dibasic acid selected from ethylene glycol diacetate and propylene glycol diacetate; dicarboxylates of glycols selected from glycol diacetates; hydroxycarboxylates selected from methyl lactate, ethyl lactate (EL), ethyl glycolate, and ethyl 3-hydroxypropionate; ketone esters selected from methyl pyruvate and ethyl pyruvate; alkyloxycarboxylic acid esters selected from methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl 2-hydroxy-2-methylpropionate, and methyl ethoxypropionate; ketone derivatives selected from methyl ethyl ketone, acetylacetone, cyclopentanone, cyclohexanone, and 2-heptanone; diacetone alcohol methyl ether; ketone alcohol derivatives selected from acetol and diacetone alcohol; ketals or acetals selected from 1,3 dioxalane and diethoxypropane; butyrolactone; amides selected from dimethylacetamide and dimethylformamide; and anisole.

[0062] In another aspect of the composition, the organic spin-coat solvent is a mixture of PGME and PGMEA. In one aspect of this embodiment, it consists of about 50% by weight PGME to about 80% by weight PGMEA, and about 20% by weight PGMEA to about 80% by weight PGMEA. In one aspect of this embodiment, it consists of about 70% by weight PGME and about 30% by weight PGMEA.

[0063] In another aspect of the compositions, they may additionally contain a surfactant as an additive to facilitate coating.

[0064] Methods of Using the Compositions of the Invention Another aspect of the present invention is a method for forming a liquid crystal (LC) self-assembled monolayer (SAM) selectively on non-metallic regions in a hybrid substrate containing both metallic and non-metallic regions, the method comprising the steps of: i) spin-coating any one of the disclosed compositions onto a hybrid substrate, wherein the liquid crystal has a polar anchor group (800) that is an alkyl-polyol coordinating moiety or at least one alkylene hydroxy-containing moiety, as described herein, and the non-metallic regions are selected from silicon dioxide, silicon with a native oxide, silicon nitride, and silicon oxynitride, and the metallic regions are selected from the group consisting of tungsten, gold, silver, copper, cobalt, ruthenium, zirconium, titanium, and hafnium; ii) baking under inert gas at a temperature ranging from about 150°C to about 180°C for about 2 minutes to about 10 minutes; iii) washing with an organic spin coating solvent; iv) air drying the substrate; v) repeating steps i) to iv) twice to obtain a self-assembled monolayer of liquid crystal on both the metallic and non-metallic areas; vi) washing the substrate with a dilute aqueous solution of acid to selectively remove the self-assembled monolayer of liquid crystal on metal areas; vii) rinsing the substrate with water and air drying to obtain a substrate in which only the non-metallic regions have a SAM of LC; The method comprises:

[0065] "Repeating steps i) through iv) twice" in step v) means that the method includes completing steps i) through iv) at least three times in total.

[0066] In one aspect of the method, the liquid crystal has a polar graft group that is an alkyl-polyol ligand moiety or a moiety containing at least one alkylene hydroxyl selected from the group consisting of Structure (Ip), Structure (Ipa), Structure (IIp), and Structure (IIpa) (wherein L1 and L2 are independently selected from a C2-C4 linear alkylene spacer, and *** is the point of attachment of the polar anchor group to the liquid crystal compound). In another aspect of this embodiment, the polar graft group (800) has Structure (Ip), in others it has Structure (Ipa), in others it has Structure (IIp), and in others it has Structure (IIpa). In one aspect of the embodiment having Structure (Ip), L1 is a C2 linear alkylene group, in others it is a C3 linear group, and in others it is a C4 linear alkylene group. In one aspect of the embodiment having structure (Ipa), L1 is a C2 linear alkylene group, in others it is a C3 linear group, and in others it is a C4 linear alkylene group. In one aspect of the embodiment having structure (IIp), L2 is a C2 linear alkylene group, in others it is a C3 linear group, and in others it is a C4 linear alkylene group. In one aspect of the embodiment having structure (IIpa), L2 is a C2 linear alkylene group, in others it is a C3 linear group, and in others it is a C4 linear alkylene group.

[0067] [ka] In another aspect of this method, the liquid crystal is selected from the group consisting of those having structures (M1), (M2), (M3), (M4), (M5), and (M7). In one more specific embodiment, the liquid crystal has structure (M1), in others it has structure (M2), in others it has structure (M3), in others it has structure (M4), in others it has structure (M5), and in others it has structure (M7).

[0068] Another aspect of the present invention is a method for selective atomic layer deposition on metal regions of a hybrid substrate containing both metal and non-metal regions, comprising the steps of: ia) producing a hybrid substrate in which the non-metallic regions have a self-assembled monolayer of a liquid crystal according to the above method using any one of the compositions described herein, said liquid crystal having a polar anchor group (800) which is either an alkyl-polyol coordinating moiety or at least one alkylene hydroxy; iia) depositing a metal oxide using atomic layer deposition techniques more selectively on metal areas that do not have a liquid crystal self-assembled monolayer; The method comprises:

[0069] In one more specific aspect of this method, the polar anchor group (800) is selected from the group consisting of Structure (Ip), Structure (Ipa), Structure (IIp), and Structure (IIpa) described herein.

[0070] In one more specific aspect of this method, the liquid crystal has structure (M1), (M3), (M4), (M5), or (M7) described herein. In one aspect of this embodiment, it has structure (M1). In another aspect of this embodiment, it has structure (M3). In another aspect of this embodiment, it has structure (M4). In another aspect of this embodiment, it has structure (M5). In another aspect of this embodiment, it has structure (M7).

[0071] In one more specific aspect of this method, the atomic layer deposition technique employs about 10 to about 50 deposition cycles, where each cycle employs a vapor treatment with (MeCp)Hf(OMe)Me for about 1 to about 5 seconds, followed by a treatment with N for about 5 to about 15 seconds, a treatment with HO for about 1 to about 5 seconds, and a treatment with N for about 5 to about 15 seconds, at a temperature of about 250° C. to about 350° C.

[0072] Another aspect of the present invention is a method for forming a liquid crystal (LC) self-assembled monolayer (SAM) selectively on metal regions in a hybrid substrate containing both metal and non-metal regions, comprising the steps of: ib) spin-coating any one of the compositions described onto a hybrid substrate, wherein the liquid crystal has polar anchor groups (800) selected from the group consisting of phosphonate ester-containing moieties, phosphonic acid-containing moieties, thiol-containing moieties, and amino-containing moieties, and further wherein the non-metallic regions are selected from silicon dioxide, silicon with a native oxide, silicon nitride, and silicon oxynitride, and the metallic regions are selected from the group consisting of tungsten, gold, silver, copper, cobalt, ruthenium, zirconium, titanium, and hafnium; iib) baking under inert gas at a temperature ranging from about 150°C to about 180°C for about 2 minutes to about 10 minutes; iiib) washing with an organic spin coating solvent; ivb) air drying the substrate; vb) repeating steps ib) through ivb) twice; vib) air drying the substrate to obtain a self-assembled monolayer of liquid crystal only on the metal areas of said substrate; The method comprises:

[0073] In another aspect of this method, the polar group (800) is selected from those having structure (IIIp), structure (IVp), structure (Vp), structure (VIp), structure (VIIp), structure (VIIIp), and structure (IXp), described herein.

[0074] In another aspect of this method, the liquid crystal is selected from the group consisting of those having structures (M8), (M9), (M10), (M11), (M12), (M13), and (M14) described herein. In one more specific embodiment, the liquid crystal has structure (M1), in others it has structure (M8), in others it has structure (M9), in others it has structure (M10), in others it has structure (M11), in others it has structure (M12), in others it has structure (M13), and in others it has structure (M14).

[0075] Another aspect of the present invention is a method for selective atomic layer deposition on metal regions of a hybrid substrate containing both metal and non-metal regions, comprising the steps of: ic) producing a hybrid substrate having a self-assembled monolayer of a liquid crystal in a metal region according to the above method using any one of the compositions described herein, said liquid crystal having a polar anchor group (800) selected from those having structure (IIIp), structure (IVp), structure (Vp) described herein, or producing a hybrid substrate having a self-assembled monolayer of a liquid crystal in a metal region according to the above method using any one of the compositions comprising the more specific liquid crystals of this type described above; iia) depositing a metal oxide using atomic layer deposition techniques more selectively on non-metallic areas that do not have a liquid crystal self-assembled monolayer; The method comprises:

[0076] In one more specific aspect of this embodiment, the atomic layer deposition technique employs about 10 to about 50 deposition cycles, where each cycle employs a vapor treatment with (MeCp)Hf(OMe)Me for about 1 to about 5 seconds, followed by a treatment with N for about 5 to about 15 seconds, a treatment with HO for about 1 to about 5 seconds, and a treatment with N for about 5 to about 15 seconds, at a temperature of about 250° C. to about 350° C. [Example]

[0077] More specific embodiments of the present disclosure and experimental results supporting such embodiments are described below. These examples are provided below to more fully explain the disclosed invention, and should not be construed as limiting the disclosed invention in any way.

[0078] It will be apparent to those skilled in the art that various modifications and variations can be made to the disclosed invention and the specific examples provided herein without departing from the spirit or scope of the disclosed invention. Thus, the disclosed invention, including the description provided by way of example below, is intended to cover modifications and variations of the disclosed invention that come within the scope of any claims and their equivalents.

[0079] Although the disclosed and claimed invention has been described and illustrated with a certain degree of detail, it will be understood that this disclosure is made by way of example only and that those skilled in the art may resort to numerous variations in the conditions and order of the steps without departing from the spirit and scope of the disclosed and claimed invention.

[0080] chemicals Unless otherwise indicated, all chemicals were purchased from Sigma-Aldrich (3050 Spruce Street, St. Louis, MO 63103).

[0081] Equipment configuration Ellipsometry Ellipsometry thickness measurements were performed using a J.A. Woollam. SAM FT was measured using a single layer model with an organic layer RI of 1.45.

[0082] X-ray photoelectron spectroscopy (XPS) measurement These were performed using a Thermo Fisher K Alpha. Experiments were performed using a pass energy of 50 eV, a step size of 0.100 eV, a dwell time of 50 ms, and 10 scans per element.

[0083] Water contact angle (WCA) measurement These were performed at room temperature using a Cruz Dynamic Contact Angle Measurement Tool. A 4 microliter drop of deionized water was used. Reported values ​​are the average of measurements from 5 to 6 spots per 1 x 1 inch coupon.

[0084] DSC measurement DSC measurements of glass transition temperature were performed using a TA Instruments DSC2500 under nitrogen with a heating and cooling cycle of 10°C / min. g ) was measured in the first heating scan from 0 to 300°C. The midpoint of the endothermic transition was considered. In characterizing liquid crystal compounds by DSC, the following abbreviations were used to denote the different physical phase transitions of liquid crystals: T g = glass transition, N = nematic phase transition, Sm = smectic phase transition, SmA = smectic A phase transition, SmB = smectic B phase transition, SmC = smectic C phase transition, I = isotropic phase transition.

[0085] 1 H NMR 1 1 H NMR spectra were recorded in CDCl 3 on a Bruker Advanced III 400 MHz spectrometer.

[0086] Si / SiOx wafer The 6-inch and 8-inch wafers were obtained from Silicon Valley Microelectronics (SVM).

[0087] X-ray reflectance (XRR) measurements These measurements were carried out at the Technical University of Darmstadt, Germany.

[0088] Spin-coated monolayer (SML) formulations were prepared by dissolving the LCC precursor in EBR7030 (a mixture of PGMEA and PGME). A 1 wt% solution was prepared and filtered using a 0.2 micron filter. SAMs were prepared on SiOx, copper, tungsten, cobalt, and ruthenium substrates using a three-step spin-coat-bake-rinse protocol as follows: The solution was spin-coated at 1500 rpm and baked at 170 °C for 5 min under nitrogen, washed with excess EBR, blown dry, and used for further analysis. SMLs with hydroxyl anchor groups were used to prepare SAMs on SiOx. The theoretical and experimental film thicknesses (ellipsometry, VASE) and WCAs for a series of SAMs are listed in Table 1. As can be seen from this table, the film thickness values ​​are larger than the theoretical values, while the WCAs are greater than 90°, suggesting a hydrophobic surface due to the nonpolar alkyl tail groups. The film thickness and molecular density were calculated using X-ray reflectivity analysis. As shown in Table 2, the XRR FT values ​​are smaller than those obtained by ellipsometry. Furthermore, the nm 2 The molecular value per mole suggests a moderate packing density. As a result of the moderate packing density, the SAM molecules exhibit relatively moderate thermal stability, and TGA indicates that the SAM begins to decompose above 270 °C. Passivation properties were measured for ALD of hafnium oxide using MeCp)2Hf(OMe)Me (2 s), N2 (10 s), HO (2 s), N2 (10 s) per cycle at 300 °C. The SML200 series SAMs show passivation up to 50 cycles for ALD of HfOx. Moderate passivation is achieved due to the moderate SAM packing density. Comparison of single and dipodal hydroxyl groups indicates that dipodal hydroxyl groups are necessary to obtain adequate SAM packing density.

[0089] Formulations SML-301, SML-302, SML-402 to SML-407, SML351, and SML-352 (using LCCs of structures (M8), (M9), (M12), (M17), (M10), and (M11), respectively) with thiol, amino, and diethylphosphonate anchor groups were used for selective SAM deposition on metal surfaces. SAMs were prepared at a bake temperature of 170 °C. Tables 1–3 and Figure 5 show the selective assembly of SML-302, SML-352, and SML-404 (structures (M9), (M11), and (M14) respectively) on metals relative to SiOx. Figure 6 shows the ALD passivation of SML-302 and SML-404 (structures (M9) and (M14) respectively) on copper, tungsten, and SiOx. The passivation data suggest that the SAM packing density follows the reactivity order thiol > amino > diethylphosphonate. Copper exhibits better packing density than tungsten. The SAM packing density reflects the passivation properties of HfOx for ALD. Given the moderate thermal stability of the SAMs, the passivation properties were measured at 200 °C. For SML-302, SML-404, and SML-406 (prepared from LCCs with structures (M9), (M14), and (M16), respectively), the passivation of copper corresponds to approximately 6 nm of HfOx. The passivation properties of SML-406 (M16) were compared on different metals, indicating Co > Cu > W > Ru, suggesting the corresponding SAM packing densities. The FTs measured and reported in Tables 1–3 were measured using ellipsometry (VASE). The TGA analyses reported here were performed using a heating rate of 10 °C / min. Water contact angles (WCA) were also measured.

[0090] [ka]

[0091] [Table 1]

[0092] The FT measured and reported in Table 1 were measured using ellipsometry (VASE). TGA analysis using a heating rate of 10 °C / min, water contact angle (WCA)

[0093] [Table 2]

[0094] Figure 4 shows the relative stability of SAMs, measured via the change in water contact angle (WCA) as a function of increasing temperature. The materials were heated under nitrogen for 5 minutes at each of the different temperatures shown on the graph. These measurements reveal the following order of thermal stability: SML-204 > SML-207 > SML-202 > SML-201 > SML-205 > SML-203. All SAMs exhibited good stability up to 250 °C. Relative LC-SAM stability depends on the LC-SAM packing order (ring substitution) and the type of anchor group. For example, SML-205 and SML-207 have 1,2 vicinal diols, but the C2 spacer in SML-207 exhibits better stability than SML-205, which has a C3 spacer. SML-204, which has two single alcohol groups that form two chemical bonds via two separate spacer groups, has better thermal stability than SML-207. Both SML-203 and SML-207 have vicinal diols and C3 spacers, but SML-203 has ethyl and fluoro groups on the aromatic ring, which reduces the LC packing density due to steric hindrance.

[0095] Figure 5 shows the relative stability of SAMs containing hydroxy moieties as polar anchor groups, as measured via the change in XPS carbon atom % after heating them under nitrogen at different temperatures for 5 minutes. XPS analysis shows relative C atomic % (at.%) percentage values. SML-205 and SML-207 exhibit higher C at.% due to the higher carbon content of their molecular composition. At 250 °C, the relative change in C at.% is very small for all SAMs because, after surface chemical bonds are broken, the SAMs still reside on the surface and contribute to the total C at.%.

[0096] Figure 6 shows the results of a study on the passivation properties of dielectric SAMs against atomic layer deposition of hafnium oxide on SML-201 to SML-207 at 300 °C. This study showed that SML-205 (M5) was the most resistant to hafnium oxide deposition after 100 cycles, followed by SML-204 (M4), SML-207 (M7), SML-202 (M2), and SML-201 (M1).

[0097] Table 3 shows water contact angle studies conducted to measure the extent of SAM formation on metal substrates, W and Cu, compared with native oxide-containing Si. Three SAM materials, SML-302 (M9), SML-352 (M11), and SML-404 (M14), were compared. These had thiol, diethylphosphonate, or amino anchoring groups, respectively. These functional groups were observed to react selectively with metal surfaces relative to SiOx.

[0098] Figure 7 shows the results of XPS studies performed on Si, W, and Cu substrates, which showed that the normalized C at.% was relatively high for both W and Cu, but very low for Si. This demonstrated that the SAM selectively grafted onto the metal surface in the order Cu>>W>>>Si.

[0099] [Table 3]

[0100] Figure 8 shows the passivation results performed, showing the relative passivation properties of SML-302 and SML-404 against ALD of HfOx at 200 °C after 100, 200, and 300 cycles. This study shows that SML-404 exhibits better passivation than SML-302. Furthermore, the passivation order is Cu>>W>>>Si.

[0101] Table 4 shows the results of water contact experiments conducted to confirm the selectivity of SML-406 (M16) with amino anchoring sites on different metal substrates. These results indicate that the relative order of WCA is Ru>W>Cu>>Si.

[0102] Figure 9 shows the passivation of the LC-SAM, SML-406, upon atomic layer deposition of HFOx at 200 °C on various metals: W, Cu, Co, and Ru. This shows that the relative order of passivation is Co>Cu>>W>>Ru>>>>Si.

[0103] [Table 4]

[0104] Synthesis of LCC SAM precursor Manufacturing of LCC (SML-201) of structure (M1) Step 3 in the synthesis of LCC of structure (M1) Scheme 1 outlines step 3 in the synthesis of LCC of structure (M1). Specifically, a solution of 2-[2-[3-ethyl-4-[4-(4-pentylcyclohexyl)phenyl]phenyl]ethyl]-propanedioate (17.86 g, 34.29 mmol) in THF (75 mL) was added dropwise to LiAlH (1.90 g, 50.06 mmol) in toluene (15 mL). The mixture was stirred at 65 °C for 1 hour, after which a small amount of water, methyl tert-butyl ether (MTBE), and dilute HCl were added. The phases were separated, and the aqueous phase was extracted with MTBE. The combined organic phases were dried over NaSO, filtered, and the solvent was removed under reduced pressure. Further purification by column chromatography (silica gel, heptane / ethyl acetate: 1 / 4) gave diethyl 2-[2-[3-ethyl-4-[4-(4-pentylcyclohexyl)phenyl]phenyl]ethyl]-propanedioate as a colorless solid (11.0 g, 25.19 mmol, HPLC: 99.4%) in 73% yield. 1H-NMR(CDCl3,500MHz):δ=7.23-7.19(m,4H),7.13-7.11(m,2H),7.05-7.03(m,1H),3.91-3.87 (m,2H),3.77-3.72(m,2H),2.73-2.65(m,2H),2.58(q,J=7.5Hz,2H),2.53-2.47(m,1H),2.16- 2.11(m,2H),1.99-1.92(m,2H),1.89-1.82(m,3H),1.71-1.62(m,2H),1.49(qd,J=12.8Hz,J=3 .3Hz,2H),1.36-1.20(m,9H),1.10(t,J=7.5Hz,3H),1.09-1.07(m,1H),0.90(t,J=7.0Hz,3H). APCI-MS:m / z:437.3. DSC:T g -67℃,79℃ Sm,112℃ SmA,122℃ I.TGA:T 5%loss =303℃.

[0105] [ka] Scheme 1 Manufacturing of LCC (SML-201) of structure (M1) Step 3 in the synthesis of LCC of structure (M1) Scheme 2 shows a general outline of the second step in the synthesis of LCC of structure (M1); specifically, diethyl malonate (6.4 mL, 0.042 mol) and 2-[3-ethyl-4-[4-(4-pentylcyclohexyl)phenyl]phenyl]ethyl methanesulfonate (9.6 g, 0.021 mol) were added to a solution of sodium ethylate (2.8 g, 0.042 mol) in ethanol (30 mL) and stirred at 75 °C overnight. The mixture was allowed to cool to room temperature, after which water was added. The aqueous phase was extracted with MTBE, and the combined organic phases were dried over NaSO, filtered, and the solvent was removed under reduced pressure. Further purification by column chromatography (silica gel, heptane / ethyl acetate: 9 / 1) gave diethyl 2-[2-[3-ethyl-4-[4-(4-pentylcyclohexyl)phenyl]phenyl]ethyl]-propanedioate as a colorless oil (11.8 g, 0.011 mol, HPLC: 99.0%) in 53% yield.

[0106] 1 H-NMR(CDCl3,500MHz):δ=7.23-7.19(m,4H),7.13-7.11(m,2H),7.05-7.03(m,1H),4 .24-4.19(m,4H),3.39(t,J=7.5Hz,2H),2.68(dd,J=8.9Hz,J=6.7Hz,2H),2.58(q,J=7 .5Hz,2H),2.53-2.47(m,1H),2.28-2.24(m,2H),1.95-1.87(m,4H),1.52-1.47(m,2H) ,1.34-1.22(m,17H),1.10(t,J=7.5Hz,3H),1.09-1.07(m,1H),0.90(t,J=7.5Hz,3H). EI-MS:m / z:520.4.

[0107] [ka] Scheme 2 Step 2 in the synthesis of LCC of structure (M1) Scheme 3 shows a general outline of the second step in the synthesis of LCC of structure (M1). Specifically, pyridine (15.9 mL, 197.0 mmol) was added to a solution of 2-[2-ethyl-4'-(4-pentyl-cyclohexyl)-biphenyl-4-yl]-ethanol (13.7 g, 35.83 mmol) and 4-(dimethylamino)-pyridine (0.9 g, 7.17 mmol) in dichloromethane (70 mL). Methanesulfonyl chloride (8.3 mL, 107.5 mmol) was added at 0°C, and the resulting solution was stirred overnight at room temperature. The mixture was diluted with water, and the aqueous phase was extracted with dichloromethane. The combined organic phases were washed with 2N HCl and water and dried over sodium sulfate. Further purification by column chromatography (silica gel, dichloromethane) gave 2-[3-ethyl-4-[4-(4-pentylcyclohexyl)phenyl]phenyl]ethyl methanesulfonate as a colorless solid (13.3 g, 29.0 mmol, HPLC: 99.3%) in 81% yield.

[0108] [ka] Scheme 3 Step 1 in the synthesis of LCC of structure (M1) Scheme 4 shows a general outline of the first step in the synthesis of an LCC of structure (M1). Specifically, a very small amount of iodine was added to a mixture of Mg (1.97 g, 0.081 mol) in THF (10 mL) and heated to 50°C. A solution of 4-bromo-2-ethyl-4'-(4-pentyl-cyclohexyl)-biphenyl (24.6 g, 0.058 mol) (prepared as described by Masakazu Yano et al., JP2017025007) in THF (180 mL) was added, and the mixture was stirred at 70°C for 3 hours. After cooling to -20°C, a cold solution of ethylene oxide (3.32 g, 0.081 mol) in THF (20 mL) was slowly added, and the mixture was stirred at -20°C for an additional 30 minutes. The mixture was diluted with THF (200 mL) and stirred at room temperature overnight. After cooling to -5 °C, water (600 mL) was slowly added. The resulting precipitate was dissolved by adding HCl. MTBE was added and the organic phase was separated. The aqueous phase was extracted with MTBE, and the combined organic phases were dried over Na2SO4, filtered, and the solvent was removed under reduced pressure. Further purification by column chromatography (silica gel: heptane / ethyl acetate: 9 / 1) gave 2-[2-ethyl-4'-(4-pentyl-cyclohexyl)-biphenyl-4-yl]-ethanol (21.8 g, 0.057 mol, 99% yield, HPLC: 99.0%).

[0109] [ka] Scheme 4 Manufacturing of LCC (SML-202) for structure (M2) Step 4 in the synthesis of LCC of structure (M2) Scheme 5 shows a general outline of the fourth step in the synthesis of LCC of structure (M2). Specifically, a solution of 2-[2-(2-fluoro-4'-propyl-biphenyl-4-yl)-ethyl]-malonic acid diethyl ester (4.80 g, 11.20 mmol) in THF (20 mL) was added dropwise to LiAlH (0.55 g, 14.49 mmol) in toluene (4 mL). The mixture was stirred at 65 °C for 1 h, after which a small amount of water, MTBE, and dilute HCl were added. The phases were separated, and the aqueous phase was extracted with MTBE. The combined organic phases were dried over NaSO, filtered, and the solvent was removed under reduced pressure. Recrystallization from heptane provided pure 2-[2-(2-fluoro-4'-propyl-biphenyl-4-yl)-ethyl]-propane-1,3-diol as a colorless solid (1.70 g, 5.37 mmol, HPLC: 99.6%) in 45% yield. 1 H-NMR (DMSO-d6,400MHz):δ=7.46-7.37(m,3H),7.28(d,J=8.1Hz,2H),7.15-7.09(m,2H),4.43(t,J=5.2H) z,2H),2.66(dd,J=9.2Hz,J=6.6Hz,2H),2.59(t,J=7.6Hz,2H),1.69-1.47(m,5H),0.92(t,J=7.3Hz,3H). EI-MS:m / z:316.1. DSC:66℃ SmC,73℃ I.TGA:T 5%loss =258℃.

[0110] [ka] Scheme 5 Manufacturing of LCC (SML-202) for structure (M2) Step 3 in the synthesis of LLC of structure (M2) Scheme 6 shows a general outline of the third step in the synthesis of LCC of structure (M2). Specifically, diethyl malonate (6.4 mL, 0.06 mol) and sodium ethylate (24.00 mL, 0.06 mol, 20% solution in ethanol) were added to a stirred solution of 4-(2-bromo-ethyl)-2-fluoro-4'-propyl-biphenyl (10.00 g, 0.03 mol) in ethanol (11 mL). After stirring overnight at 75 °C, the mixture was allowed to cool to room temperature, and water was added. The aqueous phase was extracted with MTBE, and the combined organic phases were dried over NaSO, filtered, and the solvent was removed under reduced pressure. Further purification by column chromatography (silica gel, heptane / ethyl acetate: 9 / 1) gave 2-[2-(2-fluoro-4′-propyl-biphenyl-4-yl)-ethyl]-malonic acid diethyl ester as a colorless oil (4.8 g, 0.01 mol, GC: 99.7%) in 40% yield. 1 H-NMR (CDCl3,500MHz): δ=7.45(dq,J=8.4Hz,J=2.1Hz,2H),7.38(t,J=8.0Hz,1H ),7.24(d,J=8.2Hz,2H),7.02(dd,J=7.8Hz,J=1.7Hz,1H),6.98(dd,J=11.6Hz,J= 1.7Hz,1H),4.24-4.15(m,7H),2.69(dd,J=8.8Hz,J=6.5Hz,2H),2.62(dd,J=8.6H z,J=6.8Hz,2H),1.72-1.62(m,2H),1.28(t,J=7.2Hz,6H),0.97(t,J=7.3Hz,3H). EI-MS: m / z: 400.2.

[0111] [ka] Scheme 6 Step 2 in the synthesis of LCC of structure (M2) Scheme 7 shows a general outline of the second step in the synthesis of LCC of structure (M2); specifically, 2-(2-fluoro-4'-propyl-biphenyl-4-yl)-ethanol (11.6 g, 0.04 mol) was refluxed in HBr (40.00 mL, 0.35 mol, 47%) for 16 h. Water and MTBE were added to the cooled reaction mixture, and the organic phase was washed with water and NaHCO3 solution. Further purification by column chromatography (silica gel, heptane) gave 4-(2-bromo-ethyl)-2-fluoro-4'-propyl-biphenyl (10.0 g, 0.03 mmol) in 69% yield.

[0112] [ka] Scheme 7 Step 1 in the synthesis of LCC of structure (M2) Scheme 8 shows a general outline of the first step in the synthesis of LCCs of structure (M2). Specifically, n-BuLi (88.00 mL, 0.14 mol, 15% in hexane) was added dropwise to a solution of 4-bromo-2-fluoro-4'-propyl-1,1'-biphenyl (41.10 g, 0.14 mol) in diethyl ether (400 mL) at -78 °C and stirred at this temperature for an additional 30 min. Ethylene oxide (5.17 mL, 0.11 mol) was added at -78 °C. After stirring at -78 °C for 1 h, BF3·Et2O (27.90 mL, 0.11 mol, 48%) was added within 1 h. The solution was then allowed to warm to -20 °C, quenched with saturated ammonium chloride solution, and the aqueous phase was extracted with MTBE. The combined organic phases were dried over Na2SO4, filtered, and the solvent was removed under reduced pressure. After purification by column chromatography, 2-(2-fluoro-4'-propyl-biphenyl-4-yl)-ethanol (12.6 g, 0.05 mol) was obtained as a colorless solid in 46% yield. 1H-NMR (CDCl3,500MHz): δ=7.46(dq,J=8.4Hz,J=2.1Hz,2H),7.38(t,J=8.0Hz,1 H),7.26(d,J=8.2Hz,2H),7.07(dd,J=7.8Hz,J=1.8Hz,1H),7.04(dd,J=11.5Hz ,J=1.7Hz,1H),3.91(q,J=6.4Hz,2H),2.90(t,J=6.5Hz,2H),2.63(dd,J=8.6Hz ,J=6.8Hz,2H),1.76-1.62(m,2H),1.51(t,J=5.8Hz,1H),0.98(t,J=7.3Hz,3H). EI-MS:m / z:258.0

[0113] [ka] Scheme 8 (M3) Structure LCC Manufacturing (SML-203) The LCC of structure (M3), i.e., 2-[2-[3-ethyl-4-[2-fluoro-4-[2-(4-pentylphenyl)ethyl]phenyl]phenyl]ethyl]-propane-1,3-diol, was prepared as described in Archetti, Graziano et al., WO2014 / 094959A1 (Patent Document 2).

[0114] [ka] Manufacturing of LCC (SML-204) with structure (M4)

[0115] [ka] Step 3 in the synthesis of LCC of structure (M4) In the third step in the synthesis of (M4), tetra-n-butylammonium fluoride (35.00 mL, 35.00 mmol, 1 M THF solution) was added to a solution of tert-butyl-[2-[2-[2-[tert-butyl-(dimethyl)silyl]oxy-ethoxy]-4-(4-pentylphenyl)phenoxy]ethoxy]-dimethyl-silane (8.50 g, 14.69 mmol) in THF (100 mL). The solution was stirred at room temperature for 2 hours, after which it was poured into water, acidified with 2 N HCl, and extracted with ethyl acetate. Further purification by recrystallization from toluene / ethyl acetate and column chromatography (silica gel, toluene / ethyl acetate: 1 / 3) gave 2-[2-(2-hydroxyethoxy)-4-(4-pentylphenyl)phenoxy]ethanol as a colorless solid (3.30 g, 9.55 mmol, HPLC: 99.7%) in 65% yield.

[0116] 1 H-NMR (CDCl3,500MHz): δ=7.45(d,J=8.2Hz,2H),7.22(d,J=8.2Hz,2H),7.21-7.12(m,2H),6.99(d,J=8.3Hz,1H),4.43(td,J=6.1Hz,J =2.0Hz,2H),4.16-4.12(m,4H),3.92-3.89(m,4H),2.62(t,J=7.7Hz,2H),1.69-1.60(m,2H),1.41-1.28(m,4H),0.90(t,J=7.0Hz,3H). EI-MS:m / z:344.1. DSC:128℃ I.TGA:T 5%loss =273℃.

[0117] Step 2 in the synthesis of LCC of structure (M4) Scheme 9 shows a general outline of the second step in the synthesis of LCC of structure (M4). Specifically, 2-[4-bromo-2-[2-[tert-butyl(dimethyl)silyl]oxyethoxy]-phenoxy]ethoxy-tert-butyl-dimethyl-silane (13.5 g, 25.36 mmol) and (4-pentylphenyl)boronic acid (5.00 g, 26.03 mmol) were added to a stirred solution of BNaO 4H O (5.73 g, 0.04 mol) in water (40 mL). Pd(PPh) Cl (1.04 g, 1.45 mmol) and THF (150 mL) were added, and the mixture was stirred at 70 °C overnight. The mixture was allowed to cool to room temperature, after which water was added. The aqueous phase was extracted with ethyl acetate, and the combined organic phases were dried over Na SO , filtered, and the solvent was removed under reduced pressure. Further purification by column chromatography (silica gel, heptane / ethyl acetate: 95 / 5) gave tert-butyl-[2-[2-[2-[tert-butyl-(dimethyl)silyl]oxyethoxy]-4-(4-pentylphenyl)phenoxy]ethoxy]-dimethyl-silane as a colorless oil (8.70 g, 15.03 mmol, HPLC: 99.0%) in 58% yield. EI-MS: m / z: 572.4.

[0118] [ka] Scheme 9 Step 2 in the synthesis of LCC of structure (M4) Scheme 10 shows a general outline of the first step in the synthesis of LCC of structure (M4). Specifically, a solution of 4-bromobenzene-1,2-diol (10.00 g, 52.91 mmol) in DMF (50 mL) was added dropwise to NaH (5.00 g, 208.35 mmol) in DMF (170 mL) at 0 °C. The reaction mixture was stirred at room temperature for 2 h, after which (2-bromoethoxy)(tert-butyl)dimethylsilane dissolved in DMF (30 mL) was added. After stirring at room temperature for three days, the reaction mixture was poured into water, acidified with 2H HCl, and extracted with MTBE. The combined organic phases were washed with water and dried over sodium sulfate. Further purification by column chromatography (silica gel, heptane / ethyl acetate: 95 / 5) gave 2-[4-bromo-2-[2-[tert-butyl(dimethyl)silyl]oxyethoxy]-phenoxy]ethoxy-tert-butyl-dimethyl-silane as a colorless oil (18.2 g, 35.27 mmol, GC: 98%) in 67% yield. 1 H-NMR (CDCl3,500MHz): δ=6.95(d,J=2.3Hz,1H),6.90(dd,J=8.5,2.3Hz,1H),6.69(d,J=8.5Hz, 1H),3.99-3.92(m,4H),3.90-3.83(m,4H),0.81(s,9H),0.80(s,9H),0.01(s,6H),0.00(s,6H).

[0119] [ka] Scheme 10 Synthesis of LCC (SML-205) with structure (M5)

[0120] [ka] LCC of structure (M5) was prepared using the general procedure used for LCC of structure (M3) with the appropriate reagents. 1H-NMR (DMSO-d6,500MHz): δ=7.19-7.04(m,8H),4.27(t,J=5.1Hz,2H),3.43-3.30(m,4H),2.80(s,4H),2.52-2.50(m,5H),2.41(tt,J=12 .0Hz,J=3.3Hz,1H),1.84-1.72(m,4H),1.62-1.52(m,2H),1.50-1.14(m,11H),1.03(qd,J=13.8,13.3,3.7Hz,2H),0.89(t,J=7.3Hz,3H). EI-MS:m / z:422.3. DSC:155℃I.

[0121] Synthesis of LCC of structure (M7) (SML-207)

[0122] [ka] LCC of structure (M5) was prepared using the general procedure used for LCC of structure (M3) with the appropriate reagents. 1 H-NMR(CDCl3,500MHz):δ=7.15-7.07(m,8H),3.87-3.82(m,2H),3.75-3.68 (m,2H),2.87(s,4H),2.67-2.60(m,2H),2.44(tt,J=12.2Hz,J=3.3Hz,1H), 2.14(t,J=5.1Hz,2H),1.93-1.75(m,5H),1.64-1.58(m,2H),1.49-1.17(m, 7H),1.10-0.98(m,2H),0.90(t,J=7.3Hz,3H).EI-MS:m / z:408.3.DSC:163℃ SmB,173℃ SmA,178℃ I.

[0123] Synthesis of LLC (SML-301) of structure (M8)

[0124] [ka] The LCC of structure (M8), 2-[4-[4-(4-ethylcyclohexyl)cyclohexyl]-2,3-difluoro-phenoxy]ethanediol, was prepared according to the procedure of Yun, Yong-Kuk et al., WO2017045740 (Patent Document 3).

[0125] Synthesis of LCC (SML-302) with structure (M9) Step 3 in the synthesis of structure (M9) Scheme 11 shows a general outline of the third step in the synthesis of LCCs of structure (M9). Specifically, a suspension of thioacetic acid S-{3-[2-ethyl-4'-(4-pentyl-cyclohexyl)-biphenyl-4-yl]-propyl} ester (12.4 g, 27.5 mmol) in methanol (500 mL) was cooled to 2 °C. Sodium methylate (30% in methanol, 25 mL, 134.7 mmol) was added, and the reaction mixture was stirred at 0 °C for 1 h. After stirring at 15 °C for an additional 1 h, the reaction mixture was diluted with acetic acid (50% solution) and n-heptane. The aqueous phase was extracted with n-heptane. The combined organic phases were dried over NaSO and filtered. Further purification by column chromatography (silica gel, chlorobutane / heptane: 1 / 1) and flash chromatography (reverse phase, methyl tert-butyl ether) gave 3-[2-ethyl-4'-(4-pentyl-cyclohexyl)-biphenyl-4-yl]-propane-1-thiol as a colorless oil (8.3 g, 20.3 mmol, HPLC: 99.7%) in 74% yield. 1H-NMR (CDCl3,500MHz):δ=7.26-7.22(m,4H),7.16-7.12(m,2H),7.06(dd,J=7.7Hz,J=1.9Hz,1H),2.77(t,J=7.5Hz,2H),2.62(q,J=7.5Hz,4H),2.53(t t,J=12.1Hz,J=3.4Hz,1H),2.05-1.95(m,4H),1.94-1.90(m,2H),1.57-1.4 6(m,2H),1.42-1.23(m,11H),1.13(t,J=7.5Hz,3H),0.93(t,J=7.0Hz,3H). EI-MS:m / z:408.3. DSC:Tg -64℃,22℃ N,(-33.8℃) I.TGA:T 5%loss =294℃.

[0126] [ka] Scheme 11 Step 2 in the synthesis of LCC of structure (M9) Scheme 12 shows a general outline of the second step in the synthesis of LCC of structure (M9). A solution of methanesulfonic acid 3-[2-ethyl-4'-(4-pentyl-cyclohexyl)-biphenyl-4-yl]-propyl ester (18.7 g, 39.7 mmol) in DMF (200 mL) was added dropwise to a suspension of sodium thioacetate (33.8 g, 262.70 mmol) in DMF (100 mL) and stirred at room temperature for 0.5 h. The reaction mixture was poured into a mixture of toluene and water. The phases were separated, and the aqueous phase was extracted with toluene. The combined organic phases were washed with saturated NaCl solution and dried over sodium sulfate. Further purification by column chromatography (silica gel, toluene) gave thioacetic acid S-{3-[2-ethyl-4'-(4-pentyl-cyclohexyl)-biphenyl-4-yl]-propyl} ester as a brownish oil (12.5 g, 27.1 mmol, HPLC: 97.7%) in 68% yield. 1H-NMR(CDCl3,500MHz):δ=7.26-7.22(m,4H),7.16-7.12(m,2H),7.06(dd,J=7.7H z,J=1.9Hz,1H),2.96(t,J=7.3Hz,2H),2.73(dd,J=8.6Hz,J=6.8Hz,2H),2.61(q,J =7.5Hz,2H),2.53(tt,J=12.2Hz,J=3.4Hz,1H),2.38(s,3H),2.01-1.84(m,6H),1 .56-1.47(m,2H),1.38-1.25(m,8H),1.12(t,J=7.5Hz,3H),0.93(t,J=7.0Hz,3H).

[0127] [ka] Scheme 12 Step 1 in the synthesis of LCC of structure (M9) Scheme 13 shows a general outline of the first step in the synthesis of LCCs of structure (M9).

[0128] Pyridine (8.6 mL, 105.6 mmol) was added to a solution of 3-[2-ethyl-4'-(4-pentyl-cyclohexyl)-biphenyl-4-yl]-propan-1-ol (20.0 g, 50.94 mmol) [3-[2-ethyl-4'-(4-pentyl-cyclohexyl)-biphenyl-4-yl]-propan-1-ol is available from EP 2883934 (Patent Document 4)] and 4-(dimethylamino)-pyridine (0.6 g, 4.91 mmol) in dichloromethane (200 mL). Methanesulfonyl chloride (4.3 mL, 55.5 mmol) was added at 0°C, and the resulting solution was stirred overnight at room temperature. Pyridine (5.0 mL, 62.0 mmol) and methanesulfonyl chloride (2.0 mL, 25.8 mmol) were added, and the mixture was stirred at room temperature for an additional three days. The mixture was poured into dilute hydrochloric acid and stirred at room temperature for 1 hour. The aqueous phase was extracted with dichloromethane, and the combined organic phases were washed and dried over sodium sulfate. Further purification by column chromatography (silica gel, heptane / ethyl acetate: 8 / 2) gave methanesulfonic acid 3-[2-ethyl-4'-(4-pentyl-cyclohexyl)-biphenyl-4-yl]-propyl ester as a colorless solid (17.3 g, 36.6 mmol, HPLC: 99.7%) in 72% yield. 1 H-NMR(CDCl3,500MHz):δ=7.26-7.22(m,4H),7.16-7.12(m,2H),7.06(dd,J=7.7 Hz,J=1.9Hz,1H),4.31(t,J=6.9Hz,2H),3.04(s,1H),2.80(t,J=7.5Hz,2H),2.6 2(q,J=7.5Hz,2H),2.57-2.48(m,1H),2.18-2.12(m,2H),1.99-1.90(m,6H),1.5 7-1.44(m,4H),1.38-1.24(m,8H),1.13(t,J=7.6Hz,3H),0.93(t,J=7.1Hz,3H).

[0129] [ka] Scheme 13 Synthesis of LCC (SML-351) with structure (M10) Step 2 in the synthesis of LCC of structure (M10) Scheme 14 shows a general outline of the second step in the synthesis of LCC of structure (M10). Specifically, triethyl phosphite (12.5 g, 0.07 mol) was added to 4-(3-bromopropyl)-2-ethyl-4'-(4-pentylcyclohexyl)-1,1'-biphenyl (11.5 g, 0.02 mol) and stirred at 160 °C for 22 hours. Excess triethyl phosphite was removed under reduced pressure. Further purification by column chromatography (silica gel; dichloromethane / THF 9:1) gave diethyl [3-[2-ethyl-4'-(4-pentylcyclohexyl)-[1,1'-bisphenyl]-4-yl]propyl]phosphonate (5.5 g, 0.01 mol, GC: 89%) in 38% yield. 1 H-NMR(CDCl3,500MHz):δ=7.26-7.22(m,4H),7.16-7.12(m,2H),7.06-7.04 (m,1H),4.11-4.06(m,4H),2.74(t,J=7.6Hz,2H),2.61(q,J=7.6Hz,2H),2.5 3(m,1H),2.09-1.96(m,4H),1.93-1.90(m,2H),1.90-1.82(m,4H),1.57-1. 48(m,2H),1.38-1.29(m,17H),1.13(t,J=7.5Hz,3H),0.93(t,J=7.0Hz,3H).

[0130] [ka] Scheme 14 Step 1 in the synthesis of LCC of structure (M10) Scheme 15 shows a general outline of the second step in the synthesis of LCC of structure (M10). Specifically, triphenylphosphine (13.3 g, 11.2 mL, 0.05 mol) was added to a solution of 2-[2-ethyl-4'-(4-pentyl-cyclohexyl)-biphenyl-4-yl]-ethanol (10.0 g, 0.03 mol) and tetrabromomethane (17.0 g, 5.8 mL, 0.05 mol) in THF (41 mL) at 0 °C. The mixture was allowed to warm to room temperature and stirred at this temperature for 16 h. Methyl tert-butyl ether (50 mL) was added, and the phases were separated. The aqueous phase was extracted with methyl tert-butyl ether, and the combined organic phases were dried over Na2SO4. Further purification by column chromatography (silica gel, dichloromethane) afforded 4-(3-bromopropyl)-2-ethyl-4'-(4-pentylcyclohexyl)-1,1'-biphenyl (11.5 g, 0.02 mol, GC: 99.3%) in 98% yield. 1 H-NMR (DMSO-d6,500MHz):δ=7.28-7.26(m,2H),7.20-7.16(m,3H),7.08-7.05(m,2H),3.62-3.49(m,2H),2.76-2.70(m,2H),2.56- 2.51(m,3H),2.17-2.09(m,2H),1.90-1.80(m,4H),1.52-1.46(m,2H),1.36-1.16(m,9H),1.07-1.02(m,5H),0.88(t,J=7.0Hz,3H).

[0131] [ka] Scheme 15 Synthesis of LCC (SML-352) of structure (M11) Scheme 16 shows a general outline of the second step in the synthesis of LCC of structure (M11). Specifically, 2'-fluoro-4'-{2-fluoro-4'-propyl-[1,1'-biphenyl]-4-yl}-[1,1'-biphenyl]-4-amine (2.80 g, 0.70 mmol) was added to a solution of EtO·BF (0.55 mmol, 56 μL) in 48 mL of anhydrous THF at −15 °C. tert-Butyl nitrite (3.70 mL, 90%, 3.11 mmol) was added dropwise, and the mixture was allowed to warm slowly to 5 °C. The reaction mixture was stirred at room temperature until all the starting aniline was consumed. After removing the solvent under reduced pressure, anhydrous acetonitrile (146 mL), KI (11.62 g, 0.07 mol), Pd(OAc) (167 mg, 0.12 mmol), P(OEt) (5.82 g, 3.50 mmol), and CsCO (15.51 g, 0.05 mol) were added, and the reaction mixture was stirred at 80 °C for 4 h in the absence of light. Further purification by column chromatography (silica gel, dichloromethane / THF: 9 / 1) and recrystallization from toluene gave 4-[4-(4-diethoxyphosphorylphenyl)-3-fluoro-phenyl]-2-fluoro-1-(4-propylphenyl)benzene (1.04 g, 0.20 mmol, GC: 96%) as a pale yellow solid in 28% yield. 1 H-NMR(CDCl3,500MHz):δ=7.96-7.92(m,2H),7.75-7.73(m,2H),7.59-7.43(m,8H),7.32(d,J=8.2Hz,2H ),4.26-4.10(m,4H),2.69-2.66(m,2H),1.76-1.69(m,2H),1.39(t,J=7.1Hz,6H),1.02(t,J=7.3Hz,3H).

[0132] [ka] Scheme 16 Synthesis of LCC (SML-402) with structure (M12) Scheme 17 shows a general outline of the second step in the synthesis of LCC of structure (M12). Specifically, (4'-propyl[1,1'-biphenyl]-4-yl)-boronic acid (24.0 g, 0.10 mol), 4-bromo-2,6-difluoroaniline (31.2 g, 0.15 mol), and sodium carbonate (31.8 g, 0.30 mol) were suspended in a mixture of isopropanol (200 mL), water (220 mL), and toluene (280 mL). Bis[tricyclohexylphosphino]palladium(II) chloride (2.0 g, 2.8 mmol) and hydrazine hydrate (0.1 mL, 80%) were added, and the mixture was stirred at 80 °C for 8 h. After cooling to -15 °C, the precipitate was filtered off and washed with cold water. Further purification by column chromatography (silica gel, toluene / petroleum ether: 2 / 8) and recrystallization from toluene gave 2,6-difluoro-4-[4-(4-propylphenyl)-phenyl]aniline (20.7 g, 64.0 mmol, HPLC: 98.0%) as a colorless solid in 64% yield. 1 H-NMR(CDCl3,400MHz):δ=7.65-7.60(m,2H),7.57-7.52(m,4H),7.29-7.23(m,2H),7.15- 7.11(m,2H),3.78(s,2H),2.64(t,J=7.5Hz,2H),1.74-1.62(m,2H),0.98(t,J=7.3Hz,3H). EI-MS:m / z:323.1. DSC:185℃ I.TGA:T 5%loss =247℃.

[0133] [ka] Scheme 17 Synthesis of LCC (SML-403) of structure (M13) Scheme 18 shows a general outline of the second step in the synthesis of LCC of structure (M13). Specifically, 3,5-difluoro-4'-propyl[1,1'-biphenyl]-4-yl-boronic acid (27.6 g, 0.10 mol), 4-bromoaniline (25.8 g, 0.15 mol), and sodium carbonate (31.8 g, 0.30 mol) were suspended in a mixture of isopropanol (200 mL), water (220 mL), and toluene (280 mL). Bis[tricyclohexylphosphino]palladium(II) chloride (2.0 g, 2.8 mmol) and hydrazine hydrate (0.1 mL, 80%) were added, and the mixture was stirred at 80 °C for 6 h. After cooling to room temperature, the phases were separated, and the aqueous phase was extracted with toluene. Further purification by column chromatography (silica gel, toluene) and recrystallization from toluene gave 2,6-difluoro-4-[4-(4-propylphenyl)-phenyl]aniline (10.3 g, 31.8 mmol, HPLC: 99.1%) as a colorless solid in 31% yield. 1 H-NMR(DMSO-d6,300MHz):δ=7.68(d,J=8.2Hz,2H),7.49-7.41(m,2H),7.30(d,J=8.3Hz,2H),7.16-7.12 (m,2H),6.70-6.62(m,2H),5.34(s,2H),2.60(t,J=7.5Hz,2H),1.72-1.49(m,2H),0.92(t,J=7.3Hz,3H). EI-MS:m / z:323.1. DSC:105℃(99℃) I.TGA:T 5%loss =239℃.

[0134] [ka] Scheme 18 Synthesis of LCC (SML-404) of structure (M14) Step 3 in the synthesis of LCC of structure (M14) Scheme 19 shows a general outline of the third step in the synthesis of LCC of structure (M14). Specifically, [2-fluoro-4-[3-fluoro-4-(4-propylphenyl)phenyl]phenyl]boronic acid (18.5 g, 52.5 mmol), 4-bromoaniline (9.5 g, 55.0 mmol), and sodium carbonate (17.4 g, 0.16 mol) were suspended in a mixture of isopropanol (200 mL), water (220 mL), and toluene (280 mL). Bis[tricyclohexylphosphino]palladium(II) chloride (2.5 g, 3.4 mmol) and hydrazine hydrate (0.1 mL, 80%) were added, and the mixture was stirred at 80 °C for 6 h. After cooling to 0 °C, the precipitate was filtered off and washed with cold toluene. The filtrate was then extracted with toluene. The combined fractions were recrystallized from toluene / isopropanol and further purified by column chromatography (silica gel, toluene). 2'-Fluoro-4'-{2-fluoro-4'-propyl-[1,1'-biphenyl]-4-yl}-[1,1'-biphenyl]-4-amine (16.0 g, 40.1 mmol, HPLC: 98.9%) was obtained as a colorless solid in 76% yield. 1 H-NMR(CDCl3,400MHz):δ=7.55-7.36(m,10H),7.30-7.26(m,2H),6.81-6.75(m,2H),3 .79(s,2H),2.65(dd,J=8.5Hz,J=6.8Hz,2H),1.77-1.62(m,2H),0.99(t,J=7.3Hz,3H). EI-MS:m / z:399.2. DSC:139℃ N,315.2℃ I.TGA:T 5%loss =335℃.

[0135] [ka] Scheme 19 Step 2 in the synthesis of LCC of structure (M14) Scheme 20 shows a general outline of the second step in the synthesis of LCC of structure (M14). Specifically, n-butyllithium (30 mL, 80.0 mmol, 2.7 M in heptane) was added dropwise to a solution of 1-bromo-2-fluoro-4-[3-fluoro-4-(4-propylphenyl)phenyl]benzene (25.0 g, 64.6 mmol) in THF (970 mL) at −95°C. The reaction mixture was stirred at −95°C for 2 hours, after which it was allowed to warm to −80°C. The resulting solution was again cooled to −95°C, and trimethyl borate (9.3 g, 90.0 mmol) was added. After stirring at −95°C for 30 minutes, the solution was allowed to warm slowly to room temperature. Water (200 mL) was added, and the aqueous phase was adjusted to pH 2 by adding hydrochloric acid. After stirring at room temperature for 1 hour, the aqueous phase was extracted with diethyl ether and the combined organic phases were washed with dilute hydrochloric acid. The crude product was used in the next step without further purification.

[0136] [ka] Scheme 20 Step 1 in the synthesis of LCC of structure (M14) Scheme 21 shows a general outline of the first step in the synthesis of LCC of structure (M14). Specifically, 4'-propyl-2-fluoro-4-biphenylboronic acid (30.0 g, 0.12 mol), 4-bromo-3-fluoro-iodobenzene (54.2 g, 0.18 mol), and sodium carbonate (31.8 g, 0.30 mol) were suspended in a mixture of isopropanol (200 mL), water (220 mL), and toluene (280 mL). Bis[tricyclohexylphosphino]palladium(II) chloride (2.0 g, 2.8 mmol) and hydrazine hydrate (0.1 mL, 80%) were added, and the mixture was stirred at room temperature for three days. After the addition of bis[tricyclohexylphosphino]palladium(II) chloride (1.5 g, 2.1 mmol), the reaction mixture was stirred at 80 °C for 8 hours. After cooling to room temperature, the organic phase was separated, and the aqueous phase was extracted with toluene. The combined organic phases were washed with saturated NaCl solution and dried over sodium sulfate. Further purification by column chromatography (silica gel, petroleum ether) and recrystallization from petroleum ether gave 1-bromo-2-fluoro-4-[3-fluoro-4-(4-propylphenyl)phenyl]benzene as a colorless solid (41.3 g, 106.6 mmol) in 92% yield.

[0137] [ka] Scheme 21 Synthesis of LCC (SML-405) with structure (M15)

[0138] [ka] The LCC of structure (M15), 4-[(trans,trans)-4'-propyl[1,1'-bicyclohexyl]-4-yl]-benzamine, was prepared according to the procedure of Kanie, Kiyoshi et al., Chemistry Letters 1995, 24, 68 (Non-Patent Document 1).

[0139] Synthesis of LCC (SML-406) with structure (M16)

[0140] [ka] The LCC of structure (M16), 2'-fluoro-4''-propyl-[1,1':4',1''-terphenyl]-4-amine, was prepared according to the procedure of Wang, Chun-Chih et al., US Pat. No. 8,741,176 B2.

[0141] Synthesis of LCC (SML-407) of structure (M17) The LCC of structure (M17), i.e., 2'-fluoro-4"-pentyl-[1,1':4',1"-terphenyl]-4-amine, was synthesized according to the procedure described by Wang, Chun-Chih et al., US8741176B2 for 2'-fluoro-4"-propyl-[1,1':4',1"-terphenyl]-4-amine.

[0142] [ka]

Claims

1. A patterned liquid crystal monolayer structure (100) on a patterned substrate (900), comprising: The patterned substrate (900) comprises a first surface region (500) and a second surface region (400), wherein the first surface region (500) has a liquid crystal compound (300) adsorbed thereon as a self-assembled monolayer (SAM) (200), and the second surface region (400) is free of the liquid crystal compound (300); The liquid crystal compound (300) comprises a cylindrical linear organic liquid crystal core structure, the cylindrical linear organic liquid crystal core structure comprising at least one 1,4-phenylene moiety (700), the at least one 1,4-phenylene moiety (700) having attached to one end thereof a linear alkyl group (600) containing at least two carbon atoms, and attached to the other end thereof a polar anchor group (800) selected from the group consisting of a phosphonate ester-containing moiety, a phosphonic acid-containing moiety, a thiol-containing moiety, an amino-containing moiety, a moiety containing at least one alkylene hydroxyl, and an alkyl-polyol-containing moiety; In the self-assembled monolayer (200), the liquid crystal compounds (300) are aligned in the self-assembled monolayer (200) such that each liquid crystal compound in the self-assembled monolayer (200) is parallel to each other and points in the same direction, perpendicular to the patterned substrate (900) and attached to the surface region (500) only via the polar anchor groups (800); and Any of the following: when the polar anchor group (800) is an alkyl-polyol coordinating moiety or a moiety containing at least one alkylene hydroxy, the surface region (500) to which the self-assembled monolayer (200) is attached is a non-metallic inorganic silicon compound-based surface region, and the surface region (400) without the liquid crystal compound (300) is a metallic surface region, or When the polar anchor group is selected from the group consisting of a phosphonate ester-containing moiety, a phosphonic acid-containing moiety, a thiol-containing moiety, and an amino-containing moiety, the surface region (500) to which the self-assembled monolayer (200) is attached is a metallic surface region, and the surface region (400) without the liquid crystal compound (300) is a non-metallic inorganic silicon compound-based surface region, or Either The patterned liquid crystal monolayer structure (100).

2. 2. The patterned monolayer structure on a substrate of claim 1, wherein the linear alkyl group (600) is a C2-C5 alkyl.

3. The cylindrical linear organic liquid crystal core structure comprising at least two 1,4-phenylene moieties (700) is selected from the group consisting of structures (I), (II), (IIa), (III), (IV), (V), (VI), (VII), and (VIII), in which ** is the point of attachment of the linear alkyl group (600), and * is the point of attachment of the polar anchor group (800), and R １ and R ２ 3. The patterned monolayer structure on a substrate of claim 1 or 2, wherein: is independently selected from H, C1-C2 alkyl, and F. 【Chemistry 1】

4. The polar anchor group (800) is selected from the group consisting of structure (Ip), structure (Ipa), structure (IIp), and structure (IIpa), wherein L １ and L ２ are individually selected from C2-C4 linear alkylene spacers, and *** is the point of attachment of the polar anchor group to the liquid crystal compound. 【Chemistry 2】

5. The polar anchor group (800) is selected from the group consisting of structure (IIIp), structure (IVp), structure (Vp), structure (VIp), structure (VIIp), structure (VIIIp), and structure (IXp), wherein L ３ , L ４ , L ５ , L ６ and L ７ are individually selected from C2 to C4 linear alkylene spacers, *** is the point of attachment of the polar anchor group (800) to the liquid crystal compound (300), and R ｐ１ is C1-C4 alkoxy, and R ｐ２ The patterned monolayer structure on a substrate according to any one of claims 1 to 3, wherein is C1 to C4 alkyl or C1 to C4 alkoxy. 【Transformation 3】

6. 5. A patterned monolayer structure on a substrate according to any one of claims 1 to 4, wherein the liquid crystal compound (300) is selected from the group consisting of those having the structures (M1), (M2), (M3), (M4), (M5), and (M7). 【Chemistry 4】

7. 6. A patterned monolayer structure on a substrate according to any one of claims 1 to 3 and 5, wherein the liquid crystal compound (300) is selected from the group consisting of those having the structures (M8), (M9), (M10), (M11), (M12), (M13) and (M14). 【Transformation 5】

8. The surface area (500) covered with SAM is silicon oxide (SiO ２ 7. A patterned monolayer structure on a substrate according to any one of claims 1 to 4 and 6, wherein the surface region (400) is a non-metallic inorganic silicide-based surface region selected from the group consisting of silicon with a native oxide, silicon nitride (SiN) and silicon oxynitride (SiON), and the bare surface region (400) is a metal selected from the group consisting of tungsten, gold, silver, copper, cobalt, ruthenium, zirconium, titanium and hafnium.

9. The surface area (500) coated with a SAM is a metal selected from the group consisting of tungsten, gold, silver, copper, cobalt, ruthenium, zirconium, titanium and hafnium, and the bare surface area (400) is a silicon oxide (SiO ２ 8. The patterned monolayer structure on a substrate according to any one of claims 1 to 3, 5 and 7, wherein the surface region is a non-metallic inorganic silicon compound-based surface region selected from the group consisting of silicon having a native oxide film, silicon nitride (SiN) and silicon oxynitride (SiON).

10. A composition comprising a liquid crystal compound (300) and an organic spin-cast solvent, wherein the liquid crystal compound has a cylindrical linear organic liquid crystal core structure, and the cylindrical linear organic liquid crystal core structure contains at least one 1,4-phenylene moiety (700), and the at least one 1,4-phenylene moiety (700) has a linear alkyl group (600) having at least two carbon atoms bonded to one end and a polar anchor group (800) bonded to the other end.

11. The composition of claim 10, wherein the linear alkyl group (600) is a C2 to C5 alkyl.

12. The cylindrical linear organic liquid crystal core structure comprising at least two 1,4-phenylene moieties (700) is selected from the group consisting of structures (I), (II), (IIa), (III), (IV), (V), (VI), (VII), and (VIII), in which ** is the point of attachment of the linear alkyl group (600), and * is the point of attachment of the polar anchor group (800), and R １ and R ２ is independently selected from H, C1-C2 alkyl, and F. 【Transformation 6】

13. The polar anchor group (800) is selected from the group consisting of structure (Ip), structure (Ipa), structure (IIp), and structure (IIpa), wherein L １ and L ２ are individually selected from C2 to C4 linear alkylene spacers, and *** is the point of attachment of the polar anchor group (800) to the liquid crystal compound (300). 【Transformation 7】

14. The polar anchor group (800) is selected from the group consisting of structure (IIIp), structure (IVp), structure (Vp), structure (VIp), structure (VIIp), structure (VIIIp), and structure (IXp), wherein L ３ , L ４ , L ５ , L ６ and L ７ are individually selected from C2 to C4 linear alkylene spacers, *** is the point of attachment of the polar anchor group (800) to the liquid crystal compound (300), and R ｐ１ is C1-C4 alkoxy, and R ｐ２ The composition of any one of claims 10 to 12, wherein is C1 to C4 alkyl or C1 to C4 alkoxy. 【Transformation 8】

15. 14. The composition of any one of claims 10 to 12 and 13, wherein the liquid crystal compound (300) is selected from the group consisting of those having the structures (M1), (M2), (M3), (M4), (M5), and (M7). 【Chemistry 9】

16. 15. The composition of any one of claims 10 to 12 and 14, wherein the liquid crystal compound (300) is selected from the group consisting of those having the structures (M8), (M9), (M10), (M11), (M12), (M13), and (M14). 【Chemistry 10】

17. The composition according to any one of claims 10 to 12, 13 and 15, wherein the liquid crystal compound (300) has the structure (M4). 【Chemistry 11】

18. 17. The composition of any one of claims 10 to 12, 14 and 16, wherein the liquid crystal compound (300) is selected from the group consisting of those having the structures (M8), (M9), (M12), (M13) and (M14). 【Chemistry 12】

19. The composition according to any one of claims 10 to 12, 14 and 16, wherein the liquid crystal compound (300) is selected from the group consisting of those having the structures (M10) and (M11). 【Chemistry 13】

20. The organic spin-coating solvent is a single organic solvent or a mixture of at least two organic solvents, and the organic spin-coating solvent is selected from glycol ether derivatives selected from ethyl cellosolve, methyl cellosolve, propylene glycol monomethyl ether (PGME), diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, dipropylene glycol dimethyl ether, propylene glycol n-propyl ether, and diethylene glycol dimethyl ether; glycol ether ester derivatives, such as ethyl cellosolve acetate, methyl cellosolve acetate, and propylene glycol monomethyl ether acetate (PGMEA); carboxylates of monobasic acids selected from ethyl acetate, n-butyl acetate, and amyl acetate; carboxylates of dibasic acids selected from diethyl oxylate and diethyl malonate; dicarboxylates of glycols selected from ethylene glycol diacetate and propylene glycol diacetate; ketone esters selected from methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl 2-hydroxy-2-methylpropionate, and methyl ethoxypropionate; ketone derivatives selected from methyl ethyl ketone, acetylacetone, cyclopentanone, cyclohexanone, and 2-heptanone; diacetone alcohol methyl ether; ketone alcohol derivatives selected from acetol and diacetone alcohol; ketals or acetals selected from 1,3 dioxalane and diethoxypropane; butyrolactone; amides selected from dimethylacetamide and dimethylformamide; and anisole.

21. 21. The composition of any one of claims 10 to 12, 13, 15, 17 and 20, wherein the liquid crystal compound is present in an amount of from about 0.5% to about 2.0% by weight.

22. The composition of any one of claims 10 to 12, 13, 15, 17, 20 and 21, wherein the organic spin coating solvent is a mixture of PGME and PGMEA.

23. 23. The composition of any one of claims 10 to 12, 13, 15, 17, 20, 21 and 22, wherein the organic spin coating solvent is a mixture of 70% by weight PGME and 30% by weight PGMEA.

24. The organic spin-coating solvent is a single organic solvent or a mixture of at least two organic solvents, and the organic spin-coating solvent is selected from glycol ether derivatives selected from ethyl cellosolve, methyl cellosolve, propylene glycol monomethyl ether (PGME), diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, dipropylene glycol dimethyl ether, propylene glycol n-propyl ether, and diethylene glycol dimethyl ether; glycol ether ester derivatives, such as ethyl cellosolve acetate, methyl cellosolve acetate, and propylene glycol monomethyl ether acetate (PGMEA); carboxylates of monobasic acids selected from ethyl acetate, n-butyl acetate, and amyl acetate; carboxylates of dibasic acids selected from diethyl oxylate and diethyl malonate; dicarboxylates of glycols selected from ethylene glycol diacetate and propylene glycol diacetate; ketone esters selected from methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl 2-hydroxy-2-methylpropionate, and methyl ethoxypropionate; ketone derivatives selected from methyl ethyl ketone, acetylacetone, cyclopentanone, cyclohexanone, and 2-heptanone; diacetone alcohol methyl ether; ketone alcohol derivatives selected from acetol and diacetone alcohol; ketals or acetals selected from 1,3 dioxalane and diethoxypropane; butyrolactone; amides selected from dimethylacetamide and dimethylformamide; and anisole.

25. 25. The composition of any one of claims 10 to 12, 14, 16, 18 and 24, wherein the liquid crystal compound is present in an amount of from about 0.5% to about 2.0% by weight.

26. The composition of any one of claims 10 to 12, 14, 16, 18, 24 and 25, wherein the organic spin coating solvent is a mixture of PGME and PGMEA.

27. 27. The composition of any one of claims 10 to 12, 14, 16, 18, 24, 25 and 26, wherein the organic spin coating solvent is a mixture of 70% by weight PGME and 30% by weight PGMEA.

28. 1. A method for forming a liquid crystal (LC) self-assembled monolayer (SAM) selectively on non-metallic regions in a hybrid substrate containing both metallic and non-metallic regions, comprising the steps of: i) spin-coating the composition of any one of claims 10 to 12, 13, 15, 17, 20, 21, 22 and 23 onto a hybrid substrate, wherein the polar anchor group (800) is an alkyl-polyol coordinating moiety or a moiety containing at least one alkylene hydroxy, the non-metallic regions are selected from silicon dioxide, silicon with a native oxide, silicon nitride and silicon oxynitride, and the metallic regions are selected from the group consisting of tungsten, gold, silver, copper, cobalt, ruthenium, zirconium, titanium and hafnium, ii) baking under inert gas at a temperature ranging from about 150° C. to about 180° C. for about 2 minutes to about 10 minutes; iii) washing with an organic spin coating solvent; iv) air drying the substrate; v) repeating steps i) to iv) twice to obtain a self-assembled monolayer of liquid crystal on both the metallic and non-metallic areas; vi) washing the substrate with a dilute aqueous solution of acid to selectively remove the self-assembled monolayer of liquid crystal on metal areas; vii) rinsing the substrate with water and air drying to obtain a substrate in which only the non-metallic areas have LC SAMs; The method comprising:

29. 1. A method for selective atomic layer deposition on metal regions of a hybrid substrate containing both metal and non-metal regions, comprising the steps of: ia) producing a hybrid substrate in which the non-metallic regions have a liquid crystal self-assembled monolayer according to claim 28; ii) depositing a metal oxide using atomic layer deposition techniques more selectively on the metal areas that do not have a liquid crystal self-assembled monolayer; The method comprising:

30. The atomic layer deposition technique uses deposition of from about 10 to about 50 deposition cycles, where each cycle is from about 1 to about 5 seconds of (MeCp) ２ Vapor treatment with Hf(OMe)Me followed by N for about 5 seconds to about 15 seconds ２ Processing at H for about 1 second to about 5 seconds ２ Treatment with O and N for about 5 seconds to about 15 seconds ２ 30. The method of claim 29, wherein the treatment with is carried out at a temperature of from about 250°C to about 350°C.

31. 1. A method for forming a liquid crystal (LC) self-assembled monolayer (SAM) selectively on metal regions in a hybrid substrate containing both metal and non-metal regions, comprising the steps of: ib) spin-coating the composition of any one of claims 14, 16, 18, 19, 23, 24, 25 and 26 onto a hybrid substrate, wherein the polar anchor group (800) is selected from the group consisting of phosphonate ester-containing moieties, phosphonic acid-containing moieties, thiol-containing moieties, and amino-containing moieties, and the non-metallic regions are selected from silicon dioxide, silicon with a native oxide, silicon nitride, and silicon oxynitride, and the metallic regions are selected from the group consisting of tungsten, gold, silver, copper, cobalt, ruthenium, zirconium, titanium, and hafnium; iib) baking under inert gas at a temperature ranging from about 150°C to about 180°C for about 2 minutes to about 10 minutes; iiib) washing with an organic spin coating solvent; ivb) air drying the substrate; vb) repeating steps ib) to ivb) twice; vib) air drying the substrate to obtain a self-assembled monolayer of liquid crystal only on the metal areas of said substrate; The method comprising:

32. 1. A method for selective atomic layer deposition on non-metallic regions of a hybrid substrate containing both metallic and non-metallic regions, comprising the steps of: ic) producing a hybrid substrate in which the metal regions have a liquid crystal self-assembled monolayer according to claim 31; iic) depositing a metal oxide using atomic layer deposition techniques more selectively on non-metallic areas that do not have a liquid crystal self-assembled monolayer; The method comprising:

33. The atomic layer deposition technique uses deposition of from about 10 to about 50 deposition cycles, where each cycle is from about 1 to about 5 seconds of (MeCp) ２ Vapor treatment with Hf(OMe)Me followed by N for about 5 seconds to about 15 seconds ２ Processing at H for about 1 second to about 5 seconds ２ Treatment with O and N for about 5 seconds to about 15 seconds ２ 33. The method of claim 32, wherein the treatment with is carried out at a temperature of from about 250°C to about 350°C.

34. 28. Use of a composition according to any one of claims 10 to 27, or of a liquid crystal compound (300) as defined in any one of claims 1 to 9, for selectively forming a self-assembled monolayer on either the metallic or non-metallic regions of a hybrid substrate comprising both metallic and non-metallic regions.

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