Liquid crystal SAM assembled via spin coating and regioselective deposition properties thereof

Abstract

A patterned liquid crystal monolayer structure (100) on a patterned substrate (900) is described, wherein the patterned substrate comprises a surface region (500) grafted thereto by a liquid crystal compound (300) as a self-assembled monolayer (SAM) (200) and a surface region (400) on the patterned substrate that is not grafted thereto by the SAM. Also described are compositions of selected liquid crystals (200) having different types of polar anchoring groups in an organic spin casting solvent, and using the composition on a substrate containing both or one of a metallic surface region and a non-metallic inorganic silicon compound surface region (depending on the properties of a polar anchoring group on a liquid crystal compound) Methods of selectively depositing SAM and using the selective SAM deposition as a barrier layer to selectively deposit a metal oxide dielectric by ALD on regions that are not grafted by SAM.

Description

[0001] field

[0002] The disclosed subject matter relates to templates on IC substrates formed by self-assembled monolayers (SAMs) of liquid crystals having polar anchoring groups that selectively form SAMs only on certain areas of the IC substrate, compositions for forming these templates, and methods of forming these templates and using the selective SAMs as barrier layers to affect selective ALD deposition of dielectric metal oxides on areas of the IC substrate not protected by the SAMs.

[0003] Related technologies

[0004] Over the past few decades, many efforts have been made to further increase the miniaturization, cost, speed, power consumption and versatility of the silicon-based integrated circuit industry (IC). Great progress has been made in increasing the number of transistors / CPU, and today's microprocessors contain up to 4 billion transistors / small unit area. In order to build these kinds of processors, a series of operations are performed; among the process steps are lithography, etching and deposition. Lithography is a key step in the production of transistors and resistors. The main factor affecting the resolution of the obtained structure is the illumination wavelength used during lithography. The smaller the wavelength, the higher the possible resolution and the smaller the pitch size. Currently, 193nm is the smallest illumination wavelength that has been introduced in ICs, and it can provide a pitch of ~80nm; however, today's industry goal is to achieve a pitch size of a single nanometer for the same unit area.

[0005] To avoid investments in new equipment and materials, multi-patterning lithography has been introduced and has achieved a pitch of ~40nm. However, multi-patterning comes at the expense of increased number of steps, defects, cost, process time, tools, fab space, consumable materials, and manpower.

[0006] In conventional lithography methods, ultraviolet (UV) radiation can be used to expose a photoresist layer coated on a substrate or a layered substrate through a mask. Positive or negative photoresists are available, and these can also contain refractory elements such as silicon to enable dry development for conventional integrated circuit (IC) plasma processing. In positive photoresists, the UV radiation passing through the mask causes a photochemical reaction in the photoresist, such that the exposed areas are removed with a developer solution or by conventional IC plasma processing. Conversely, in negative photoresists, the UV radiation passing through the mask causes the areas exposed to the radiation to become less removable with a developer solution or by conventional IC plasma processing. Integrated circuit features such as gates, vias, or interconnects are then etched into the substrate or layered substrate, and the remaining photoresist is removed. When using conventional lithography exposure processes, the size of the integrated circuit features is limited. Due to limitations associated with aberration, focus, proximity effects, minimum achievable exposure wavelength, and maximum achievable numerical aperture, it is difficult to achieve further reduction in pattern size with radiation exposure. Directed self-assembly is a promising method that has drawn attention in overcoming some of the drawbacks of conventional lithography as outlined above. Directed self-assembly of block copolymers is a method that can be used to generate ever-smaller patterned features for manufacturing microelectronic devices with critical dimensions (CDs) where nanoscale-level features can be achieved. Directed self-assembly methods are desirable for extending the resolution capabilities of micro-lithography techniques. The demand for large-scale integration has led to the continuous shrinking of circuit sizes and features in devices. In the past, the ultimate resolution of features has depended on the wavelength of the light used to expose the photoresist, which has its own limitations. The latest technology for achieving target pitch using shorter wavelength light is extreme ultraviolet lithography (EUV), which theoretically can achieve a maximum pitch resolution of ~13.5 nm. However, this technology has a high defect rate, which does not meet industry expectations. The defect rate specific to EUV is summarized as the mask defect rate and is a combination of substrate, multilayer blank, and absorber patterning defects. In addition, this technology is particularly costly, with only 53 machines worldwide capable of production. Directed assembly techniques, such as graphoepitaxy and chemoepitaxy using block copolymer imaging, are highly desirable techniques for enhancing resolution while reducing CD variation. These techniques can be used to enhance conventional UV lithography techniques or to achieve even higher resolution and CD control in methods employing EUV, electron beam, deep UV, or immersion lithography.

[0007] Directed self-assembly (DSA) of block copolymer (BCP) lithography is an additional alternative or complement to conventional lithography, which is different from the methods mentioned above in that it involves a combination of bottom-up and top-down methods. A template created using lithography\EUV technology (top-down method) is spin-coated with BCP and then phase-separated at a very high resolution of individual nanometers (bottom-up) under the influence of a guiding pattern (template). After that, one block is selectively etched, and the desired pitch pattern is obtained according to the size of the block.

[0008] In the field of IC technology, the selective deposition of organic or inorganic materials is an important process in the IC industry, which requires selectivity specific to metals or dielectrics via direct and indirect assembly processes. One such application is the passivation of dielectric or metal surfaces on a given patterned substrate for the area-selective deposition of metal oxides via atomic layer deposition (ALD). This application requires the selective grafting of organic materials, such as self-assembled monolayers (SAMs) or chain-end functional polymers (brushes), for introducing subsequent deposition or assembly processes, enabling the passivation of the underlying selective areas. In the ALD or DSA industries, simple methods such as spin-coating organic materials that can exhibit selectivity for specific areas of a substrate in chip manufacturing lithography processes are highly sought after. Common methods for SAM deposition are solution or immersion methods and vapor-phase methods. Both methods have their respective advantages and disadvantages. The chemistry and processing of SAM precursors limit their selective deposition via spin-coating methods.

[0009] For liquid crystal display (LCD) technology, the alignment of liquid crystals (LCs) on the surface of glass or indium tin oxide (ITO) is achieved by surface modification to enable the alignment of LCs. This is achieved by surface modification with alkylsilanes and silanoxy functional groups with or without LC components. In this method, the glass or ITO surface is modified with alkoxysilane SAMs using solution dip-coating methods and vapor delivery. Liquid crystal compounds (LCCs) with functional groups such as carboxylic acid, hydroxyl, amine, and thiol are known and are used as pure materials or as mixtures with photocurable polymer matrices in liquid crystal display (LCD) technology.

[0010] 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. As the demands of the semiconductor roadmap continue to increase, which is testing the limits of past electronic materials, ALD is becoming increasingly important due to its ability to control deposition at the atomic scale and conformally deposit on structures with very high aspect ratios. For the fabrication of 3-D devices, lateral patterning using ALD is employed, for example, by using conventional photoresists and lithography techniques such as semiconductor processing, other mask polymer layers, direct-write electron beam to selectively remove the mask layer to allow ALD on that area, or by using a patterned octadecyltrichlorosilane monolayer.

[0011] There is a need for a simple spin-coatable method that is compatible with standard IC track equipment, which can easily form self-assembled monolayers (SAMs) with high-density moieties that can selectively protect metal surface regions or non-metal surface regions on an IC substrate to enhance atomic layer deposition of dielectric metal oxides in the unprotected regions and is compatible with nanoscale dimensions dictated by modern IC patterning methods such as, for example, EUV, DSA, and combinations of these techniques. Description of the Drawings

[0012] Figure 1 : Schematic of the spin-coating SAM assembly of liquid crystal molecules.

[0013] Figure 2 : Schematic depiction of a portion of a cross-section taken perpendicular to a patterned substrate, where only some portions of the substrate have a covering SAM of liquid crystal, which consists of a straight-chain alkyl group, a central core with at least two phenyl moieties, and a polar anchoring group.

[0014] Figure 3 : Schematic depiction of a liquid crystal compound (300).

[0015] Figure 4 : Thermal stability of the SAM via the change in water contact angle (heating the SAM in nitrogen at different temperatures for 5 min).

[0016] Figure 5 : Thermal stability of the SAM via the change in the percentage of carbon atoms by XPS (heating the SAM in nitrogen at different temperatures for 5 min).

[0017] Figure 6 : Passivation characteristics of the dielectric SAM for atomic layer deposition of hafnium oxide at 300 °C.

[0018] Figure 7 : Selective characterization of the SAM using XPS.

[0019] Figure 8 : Passivation characteristics of ALD for HfOx at 200 °C.

[0020] Figure 9 : Passivation characteristics of ALD for HfOx at 200 °C.

[0021] Overview

[0022] The present disclosure describes a spin-on composition that includes a liquid crystal having an anchoring group and an organic spin-on solvent, which, after being spin-coated on an IC substrate containing a metal surface region and a non-metallic inorganic silicon compound surface region, selectively forms self-assembled monolayers (SAMs) on some of these regions, changing the characteristics of these regions. Examples of non-metallic inorganic silicon regions are silicon oxide (SiO2), silicon nitride (SiN), and silicon oxynitride, while examples of metal regions are copper and tungsten. By spin-coating and baking and cleaning the film with a treatment solution ( Figure 1 ), the selective SAM monolayers on any of these surface region substrate types depend on the anchoring group and compounds with different anchoring groups (LCCs). This type of selective surface property enhancement technique enables selective passivation of atomic layer deposition of dielectric metal oxides such as titanium oxide, aluminum oxide, hafnium oxide, etc.

[0023] More specifically, the present invention relates to a template that is a patterned liquid crystal monolayer structure (100) on a patterned substrate (900), which includes:

[0024] ○ A patterned substrate (900) that includes 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) that does not contain the liquid crystal compound (300);

[0025] ■ Wherein the liquid crystal compound (300) consists of a columnar linear organic liquid crystal core structure containing at least one 1,4-phenylene moiety (700), the 1,4-phenylene moiety being attached at one end to a linear alkyl group (600) containing at least two carbons and at the other end to a polar anchoring group (800) selected from the group consisting of a moiety containing a phosphonate, a moiety containing a phosphonic acid, a moiety containing a thiol, a moiety containing an amino group, a moiety containing at least one alkyl hydroxyl group, and a moiety containing an alkyl-polyol;

[0026] ■ Wherein in the self-assembled monolayer (200), the liquid crystal compounds (300) are arranged in the self-assembled monolayer (200) such that each liquid crystal compound is parallel to each other and points in the same direction in the self-assembled monolayer (200), perpendicular to the patterned substrate (900) and attached to the surface region (500) only through the polar anchoring group (800); and

[0027] ○ Any one of the following,

[0028] ● When the polar anchoring group (800) is an alkyl-polyol coordination moiety or a moiety containing at least one alkylene hydroxyl group, the surface region (500) to which the self-assembled monolayer (200) is attached is a surface region based on a non-metallic inorganic silicon compound, and the surface region (400) that does not contain the liquid crystal compound (300) is a metal surface region, or

[0029] ● When the polar anchoring group is selected from a moiety containing phosphonate, a moiety containing phosphonic acid, a moiety containing thiol, and a moiety containing amino, the surface region (500) to which the self-assembled monolayer (200) is attached is a metal surface region, and the surface region (400) that does not contain the liquid crystal compound (300) is a surface region based on a non-metallic inorganic silicon compound.

[0030] Figure 2 A schematic depiction showing a portion of a cross-section taken perpendicular to the above template and showing the labeling explaining the above portion of the above template. The template on the substrate is made of a protective SAM of liquid crystal (which has been selectively formed only in certain regions of the substrate) to enhance atomic layer deposition (ALD) of dielectric metal oxide in those regions not covered by the SAM.

[0031] The present invention also relates to a composition comprising a liquid crystal compound (300) and an organic spin-casting solvent, wherein the liquid crystal compound consists of a columnar linear organic liquid crystal core structure containing at least one 1,4-phenylene moiety (700), the 1,4-phenylene moiety being attached at one end to a linear alkyl group (600) having at least two carbons and at the other end to a polar anchoring group (800). Figure 3 A schematic depiction showing the liquid crystal compound (300).

[0032] The present invention also relates to a method for preparing the above template and using the template to affect the selective ALD of dielectric metal oxide on the regions of the template not protected by the SAM of liquid crystal (300). Another aspect of the present invention is the use of the composition according to any one of claims 10 to 27 or the liquid crystal compound (300) as defined in any one of claims 1 to 9 for selectively forming a self-assembled monolayer on the metal or non-metal regions of a hybrid substrate comprising both metal and non-metal regions.

[0033] Details

[0034] It should be understood that both the foregoing general description and the following detailed description are illustrative and explanatory and are not restrictive of the claimed subject matter. In this application, unless otherwise specifically stated, the use of the singular includes the plural, the words "a / an" mean "at least one", and the use of "or" means "and / or". Further, the use of the term "including" and other forms such as "includes" and "included" is not restrictive. Additionally, unless otherwise specifically stated, terms such as "element" or "component" include both elements and components that contain one unit and elements or components that contain more than one unit. As used herein, unless otherwise indicated, the conjunction "and" is intended to be inclusive, and the conjunction "or" is not intended to be exclusive. For example, the phrase "or, alternatively" is intended to be exclusive. As used herein, the term "and / or" refers to any combination of the foregoing elements, including the use of a single element.

[0035] The section headings used herein should not be construed as limiting the subject matter described for organizational purposes. All documents or portions of documents cited in this application, including but not limited to patents, patent applications, articles, books, and papers, are hereby expressly incorporated by reference in their entirety for any purpose. If one or more of the incorporated literature references and similar materials define terms in a manner that contradicts the definition of such terms in this application, then this application shall control.

[0036] Unless otherwise specified, "alkyl" refers to a hydrocarbon group that can be straight-chain, branched (e.g., methyl, ethyl, propyl, isopropyl, tert-butyl, etc.), or cyclic (e.g., cyclohexyl, cyclopropyl, cyclopentyl, etc.), polycyclic (e.g., norbornyl, adamantyl, etc.). These alkyl moieties can be substituted or unsubstituted as described below. The term "alkyl" refers to such moieties having from C-1 to C-8 carbons. It should be understood that for structural reasons, straight-chain alkyls start with C-1, while branched-chain alkyls and cycloalkyls start with C-3 and polycyclic alkyls start with C-5. Further, it should be understood that unless otherwise specified, moieties derived from the alkyls described below, such as alkyloxy (alkoxy), have the same range of carbon numbers. The same criteria apply to the naming of C-1 to C-4 alkyls. If the length of the alkyl is named other than as described above, the above definition of alkyl still includes all types of alkyl moieties as described above with respect thereto, and the structural considerations regarding the minimum number of carbons for a given type of alkyl still apply.

[0037] An alkyloxy (also known as an alkoxy) is an alkyl group attached through an oxygen (-O-) moiety (e.g., methoxy, ethoxy, propoxy, butoxy, 1,2-isopropoxy, cyclopentyloxy, cyclohexyloxy, etc.). These alkoxy moieties can be substituted or unsubstituted as described below. The criteria for establishing the nature of the alkyl group in a C-1 to C-8 alkyloxy or a C-1 to C-4 alkyloxy are the same as those previously described for the alkyl moiety.

[0038] Halogenated or halo refers to a halogen, F, Cl, Br, or I, attached to an organic moiety by a single bond.

[0039] Haloalkyl refers to a straight-chain, cyclic, or branched saturated alkyl group as defined above, wherein if more than one halogenated moiety is present, at least one of these hydrogens has been replaced by a halo group selected from the group consisting of F, Cl, Br, I, or a mixture of these. Fluoroalkyl is a specific subgroup of these moieties.

[0040] Unless otherwise specified, the term "alkylene" refers to a hydrocarbon group that can be straight-chain, branched, or cyclic and has two or more attachment points (e.g., two attachment points: methylene, ethylene, 1,2-isopropyl, 1,4-cyclohexylene, etc.; three attachment points: 1,1,1-substituted methane, 1,1,2-substituted ethane, 1,2,4-substituted cyclohexane, etc.). Here again, when specifying a possible range of carbons, such as C-1 to C-20, as a non-limiting example, the range encompasses straight-chain alkylene groups starting with C-1, but only branched alkylene groups or cycloalkylene groups starting with C-3. These alkylene moieties can be substituted or unsubstituted as described below. The term straight-chain alkylene refers to a straight-chain alkylene moiety having two attachment points and is unsubstituted unless otherwise specified.

[0041] The term "acyl" refers to a (-C=O)-R moiety, where R is H, aryl, or alkyl.

[0042] The term "aryl" or "aromatic group" refers to such groups containing 6 to 24 carbon atoms, including phenyl, tolyl, xylyl, naphthyl, anthracenyl, biphenyl, terphenyl, etc. These aryl groups can be further substituted by any suitable substituent (e.g., the alkyl, alkoxy, acyl, or aryl groups mentioned above).

[0043] Unless otherwise specified herein, when referring to aryl, alkyl, alkoxy, fluoroalkyl, fluoroalkoxy, fused aromatic ring, arene, heteroarene, the term "substituted" means one of these moieties that also contains one or more substituents selected from the group consisting of: unsubstituted alkyl, substituted alkyl, unsubstituted aryl, alkoxyaryl (alkyl-O-aryl-), dialkoxyaryl ((alkyl-O-)2-aryl), haloaryl, alkoxy, alkylaryl, haloalkyl, halogen, hydroxy, cyano, nitro, acetyl, alkylcarbonyl, formyl, vinyl (CH2=CH-), phenylvinyl (Ph-CH=CH-), arylvinyl (aryl-CH=CH) and substituents containing a vinylene arylene moiety (e.g., Ar(-CH=CH-Ar-) z , where z is 1 - 3). Specific non-limiting examples of substituted aryl and substituted arylvinyl substituents are as follows, where represents the point of attachment:

[0044]

[0045] When used in the context of the SAM template of the present invention ( Figure 2 ) and the polar anchoring group of the liquid crystal molecules used in the liquid crystal composition of the present invention (schematically shown as (800) in Figure 3 ), the term moiety containing an amino group means an amino group (-NH2), which can be directly bonded to the liquid crystal molecule by a covalent bond or through a C-1 to C-8 straight-chain alkylene moiety (-alkylene-NH2) or a C-2 to C-8 straight-chain oxyalkylene moiety (-O-alkylene-NH2).

[0046] When used in the context of the SAM template of the present invention ( Figure 2 ) and the polar anchoring group of the liquid crystal molecules used in the liquid crystal composition of the present invention (schematically shown as (800) in Figure 3 ), the term moiety containing a phosphonate means a dialkylphosphonate group (-P(=O)(O-alkyl)2) moiety, which can be directly bonded to the liquid crystal molecule by a covalent bond or through a C-1 to C-8 straight-chain alkylene moiety (-alkylene-P(=O)(O-alkyl)2) or a C-2 to C-8 straight-chain oxyalkylene moiety (-O-alkylene-P(=O)(O-alkyl)2).

[0047] When used in the context of the SAM template of the present invention ( Figure 2 ) and the polar anchoring group of the liquid crystal molecules used in the liquid crystal composition of the present invention (schematically shown as (800) in Figure 3When used in the context (schematically shown as (800) in [])), the term phosphonic acid moiety refers to a phosphonic acid group (-P(=O)(OH)₂) moiety that can be directly attached to a liquid crystal molecule by a covalent bond or through a C-1 to C-8 straight-chain alkylene moiety (-alkylene-P(=O)(OH)₂) or a C-1 to C-8 straight-chain oxyalkylene moiety (-O-alkylene-P(=O)(OH)₂).

[0048] When in the SAM template of the present invention ( Figure 2 ) and in the context of the polar anchoring group of the liquid crystal molecules used in the liquid crystal composition of the present invention (as Figure 3 schematically shown as (800) in []), the term thiol-containing moiety refers to a thiol group (-SH) moiety that is attached to a liquid crystal molecule through a C-1 to C-8 straight-chain alkylene moiety (-alkylene-SH) or a C-2 to C-8 straight-chain oxyalkylene moiety (-O-alkylene-SH).

[0049] When in the SAM template of the present invention and in the context of the polar anchoring group of the liquid crystal molecules used in the liquid crystal composition of the present invention (as Figure 3 schematically shown as (800) in []), the term alkylene hydroxy-containing moiety refers to a hydroxy (-OH) moiety that is attached to a liquid crystal molecule through a C-1 to C-8 straight-chain oxy-alkylene moiety (-O-alkylene-OH) or a C-1 to C-8 straight-chain alkylene moiety (-alkylene-OH).

[0050] When in the SAM template of the present invention and in the context of the polar anchoring group of the liquid crystal molecules used in the liquid crystal composition of the present invention (as Figure 3 schematically shown as (800) in []), the term alkyl-polyol-containing moiety is an alkyl polyol (-C(alkylene-OH) n , where n is 2 or 3), which is attached to a liquid crystal molecule through a C-2 to C-8 straight-chain alkylene moiety (alkylene-C(alkylene-OH) n , where n is 2 or 3) or a C-2 to C-8 straight-chain oxyalkylene moiety (-O-alkylene-C(alkylene-OH) n , where n is 2 or 3).

[0051] The term "columnar straight-chain organic liquid crystal core structure containing at least one 1,4-phenylene moiety" (as schematically shown as (700) in Figure 3 ) contains at least one 1,4-phenylene moiety but may also contain additional different straight-chain moieties (such as additional 1,4-phenylene moieties, 1,4-cyclohexylene moieties, 1,4-phenylene, straight-chain ethylene moieties, trans-vinylidene moieties ( wherein represents the part of the attachment point on the C(H)=C(H) part), where each of these linear parts is attached to each other to form a linear arrangement in the liquid crystal molecule, which promotes the π-π interaction of one or more of the 1,4-phenylene parts in different liquid crystal molecules, and when these are grafted to a specific area of the patterned substrate through their polar anchoring groups (800), the liquid crystal molecules (300) (composed of the linear alkyl group (600), the columnar linear organic liquid crystal core structure (700) and the polar anchoring group (800)) interact through these π-π interactions( Figure 2 ). Non-limiting examples of columnar linear organic liquid crystal core structures containing at least one 1,4-phenylene part are shown in structures (I) to (VIII), as described herein.

[0052] In the SAM template of the present invention( Figure 2 ) and in the liquid crystal composition of the present invention, the term "linear alkyl group containing at least two carbons" (as schematically shown as (600) in Figure 3 ) is a linear alkyl group (also known as the normal alkyl part), which has at least two carbon atoms and is unsubstituted.

[0053] One aspect of the present invention relates to a template of the present invention, which is a patterned liquid crystal monolayer structure (100) on a patterned substrate (900), which comprises:

[0054] ○ A patterned substrate (900), which comprises a first surface area (500) having a liquid crystal compound (300) adsorbed thereon as a self-assembled monolayer (SAM) (200) and a second surface area (400) without the liquid crystal compound (300);

[0055] ■ Wherein the liquid crystal compound (300) is composed of a columnar linear organic liquid crystal core structure containing at least one 1,4-phenylene part (700), the 1,4-phenylene part is attached to a linear alkyl group (600) containing at least two carbons at one end and to a polar anchoring group (800) at the other end, and the polar anchoring group is selected from the group consisting of a part containing phosphonate, a part containing phosphonic acid, a part containing thiol, a part containing amino, a part containing at least one alkylene hydroxyl group, and a part containing alkyl-polyol;

[0056] ■ Wherein in the self-assembled monolayer (200), the liquid crystal compounds (300) are arranged in the self-assembled monolayer (200) such that each liquid crystal compound is parallel to each other and points in the same direction in the self-assembled monolayer (200), perpendicular to the patterned substrate (900) and attached to the surface area (500) only through the polar anchoring group (800); and

[0057] ○ Any one of the following,

[0058] ● When the polar anchoring group (800) is an alkyl-polyol coordination moiety or a moiety containing at least one alkylene hydroxyl group, the surface region (500) to which the self-assembled monolayer (200) is attached is a surface region based on a non-metallic inorganic silicon compound, and the surface region (400) that does not contain the liquid crystal compound (300) is a metal surface region, or

[0059] ● When the polar anchoring group is selected from a moiety containing a phosphonate, a moiety containing a phosphonic acid, a moiety containing a thiol, and a moiety containing an amino group, the surface region (500) to which the self-assembled monolayer (200) is attached is a metal surface region, and the surface region (400) that does not contain the liquid crystal compound (300) is a surface region based on a non-metallic inorganic silicon compound.

[0060] Figure 2 A schematic depiction showing a portion of a cross-section taken perpendicular to the above template and annotated to illustrate the above portion of the above template on a substrate, on which a protective SAM of liquid crystal has been selectively formed only in certain regions of the substrate. The selective formation of this SAM serves to enhance atomic layer deposition (ALD) of the dielectric metal oxide in those regions not covered by the SAM.

[0061] Another aspect of the template of the present invention is when it is a template composed of the elements (100), (200), (300), (400), (500), (600), (700), and (800) as described above and no other elements.

[0062] Another aspect of the template of the present invention is when the straight-chain alkyl group (600) is a C-2 to C-5 alkyl group. In one aspect of this embodiment, the straight-chain 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.

[0063] In another aspect of the template of the present invention, as described herein, the columnar linear organic liquid crystal core structure comprising at least two 1,4-phenylene moieties (700) is a structure selected from structures (I), (II), (IIa), (III), (IV), (V), (VI), (VII) and (VIII), where ** is the attachment point of the straight-chain alkyl group (600) and * is the attachment point of the polar anchoring 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 last embodiment, it has structure (VIII).

[0064]

[0065] In another aspect of the template of the present invention, as described herein, the polar grafting (also known as anchoring) group (800) is selected from structure (Ip), structure (Ipa), structure (IIp) and structure (IIpa), where L1 and L2 are independently selected from C2-C4 straight-chain alkylene spacers, and *** is the attachment point of the polar anchoring group to the liquid crystal compound. In another aspect of this embodiment, the polar grafting group (800) has structure (Ip), in another aspect, it has structure (Ipa), in another aspect, it has structure (IIp), in another aspect, it has structure (IIpa). In one aspect of the embodiment having structure (Ip), L1 is a C2 straight-chain alkylene, in another aspect, it is a C3 straight-chain group, in another aspect, it is a C4 straight-chain alkylene. In one aspect of the embodiment having structure (Ipa), L1 is a C2 straight-chain alkylene, in another aspect, it is a C3 straight-chain group, in another aspect, it is a C4 straight-chain alkylene. In one aspect of the embodiment having structure (IIp), L2 is a C2 straight-chain alkylene, in another aspect, it is a C3 straight-chain group, in another aspect, it is a C4 straight-chain alkylene. In one aspect of the embodiment having structure (IIpa), L2 is a C2 straight-chain alkylene, in another aspect, it is a C3 straight-chain group, in another aspect, it is a C4 straight-chain alkylene.

[0066]

[0067] In another aspect of the template of the present invention, as described herein, the polar grafting group (800) is selected from structure (IIIp), structure (IVp), structure (Vp), structure (VIp), structure (VIIp), structure (VIIIp) and structure (IXp), where L3, L4, L5, L6 and L7 are each independently selected from C-2 to C-4 straight-chain alkylene spacers, *** is the attachment point of the polar anchoring group to the liquid crystal compound, R p1 is C-1 to C-4 alkoxy, and R p2is a C-1 to C-4 alkyl or a C-1 to C-4 alkoxy group. In one aspect of this embodiment, the polar grafting group has the structure (IIIp). In another aspect of this embodiment, L3 is a C-2 straight-chain alkylene group. In yet another aspect, L3 is a C-3 straight-chain alkylene group. In still another aspect, it is a C-4 straight-chain alkylene group. In one aspect of this embodiment, the polar grafting group has the structure (IVp). In one aspect of this embodiment, L4 is a C-2 straight-chain alkylene group. In another aspect, L4 is a C-3 straight-chain alkylene group. In still another aspect, it is a C-4 straight-chain alkylene group. In one aspect of this embodiment, the polar grafting group has the structure (Vp). In one aspect of this embodiment, Rp1 is methoxy. In another aspect, it is ethoxy. In yet another aspect, it is n-propoxy. In still another aspect, it is n-butoxy. In one aspect of this embodiment, Rp2 is methyl. In another aspect, it is ethyl. In yet another aspect, it is n-propyl. In still another aspect, it is n-butyl. In another aspect of this embodiment, Rp2 is methoxy. In another aspect, it is ethoxy. In yet another aspect, it is n-propoxy. In still another aspect, it is n-butoxy. In one aspect of this embodiment, the polar grafting group has the structure (VIp). In one aspect of this embodiment, Rp1 is methoxy. In another aspect, it is ethoxy. In yet another aspect, it is n-propoxy. In still another aspect, it is n-butoxy. In one aspect of this embodiment, Rp2 is methyl. In another aspect, it is ethyl. In yet another aspect, it is n-propyl. In still another aspect, it is n-butyl. In another aspect of this embodiment, Rp2 is methoxy. In another aspect, it is ethoxy. In yet another aspect, it is n-propoxy. In still another aspect, it is n-butoxy. In another aspect of this embodiment, the polar grafting group has the structure (VIIp). In another aspect of this embodiment, the polar grafting group has the structure (VIIIp). In one aspect of this embodiment, L6 is a C-2 straight-chain alkylene group. In another aspect, it is a C-3 straight-chain alkylene group. In still another aspect, it is a C-4 straight-chain alkylene group. In another aspect of this embodiment, the polar grafting group has the structure (IXp). In one aspect of this embodiment, L7 is a C-2 straight-chain alkylene group. In another aspect, it is a C-3 straight-chain alkylene group. In still another aspect, it is a C-4 straight-chain alkylene group.

[0068]

[0069] In another aspect of the template of the present invention, as described herein, the liquid crystal compound (300) is a compound selected from compounds having structures (M1), (M2), (M3), (M4), (M5), and (M7). In one aspect of this embodiment, the liquid crystal compound (300) has structure (M1), in another aspect, it has structure (M2), in another aspect, it has structure (M3), in another aspect, it has structure (M4), in another aspect, it has structure (M5), and in another aspect, it has structure (M7).

[0070]

[0071] In another aspect of the template of the present invention, as described herein, the surface region (500) covered with SAM is a surface region based on a non-metallic inorganic silicon compound selected from silicon dioxide (SiO2), silicon with native oxide, silicon nitride (SiN), and silicon oxynitride (SiON), and the surface region (400) which is bare is a metal selected from tungsten, gold, silver, copper, cobalt, ruthenium, zirconium, titanium, and hafnium. In one aspect of this embodiment, the surface region (500) covered with SAM is a surface region based on non-metallic inorganic silicon, which is silicon dioxide (SiO2), in another aspect, it is silicon (Si) with native oxide, in another aspect, it is silicon nitride (SiN), and in another aspect, it is silicon oxynitride (SiON); in these aspects, in one aspect, the surface region (400) which is bare is tungsten, in another aspect, it is gold, in another aspect, it is silver, in another aspect, it is copper, in another aspect, it is cobalt, in another aspect, it is ruthenium, in another aspect, it is zirconium, in another aspect, it is titanium, and in another aspect, it is hafnium.

[0072]

[0073]

[0074] ​In another aspect of the template of the present invention, as described herein, the surface region (500) covered with SAM is a metal selected from tungsten, gold, silver, copper, cobalt, ruthenium, zirconium, titanium, and hafnium, and the surface region (which is bare) (400) is a surface region of a non-metallic inorganic silicon compound selected from silicon dioxide (SiO2), silicon with native oxide, silicon nitride (SiN), and silicon oxynitride (SiON). In one aspect of this embodiment, the surface region (500) covered with SAM is tungsten, in another aspect, it is gold, in another aspect, it is silver, in another aspect, it is copper, in another aspect, it is cobalt, in another aspect, it is ruthenium, in another aspect, it is zirconium, in another aspect, it is titanium, in another aspect, it is hafnium; in these aspects, in one aspect, the surface region (which is bare) (400) is silicon dioxide (SiO2), in another aspect, it is silicon (Si) with native oxide, in another aspect, it is silicon nitride (SiN), in another aspect, it is silicon oxynitride (SiON).

[0075] The composition of the present invention

[0076] 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 consists of a columnar linear organic liquid crystal core structure comprising at least one 1,4-phenylene moiety (700), the 1,4-phenylene moiety being attached at one end to a linear alkyl group (600) having at least two carbons and at the other end to a polar anchoring group (800). In one aspect of this embodiment, the composition consists of a liquid crystal compound (300) and an organic spin-casting solvent.

[0077] In another aspect of the above composition, in the liquid crystal compound (300), the linear alkyl group (600) is a C-2 to C-5 alkyl group. 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.

[0078] In another aspect of the above composition, in the liquid crystal compound (300), the columnar linear organic liquid crystal core structure containing at least two 1,4-phenylene moieties (700) is selected from structures (I), (II), (IIa), (III), (IV), (V), (VI), (VII), and (VIII), where ** is the attachment point of the linear alkyl (600) and * is the attachment point of the polar anchoring group (800), and R1 and R2 are each independently selected from H, C1 to C2 alkyl, and F. In another aspect of this embodiment, the linear organic liquid crystal core structure containing at least two 1,4-phenylene moieties (700) has structure (I); in one aspect of this embodiment, R1 is H, in another aspect, it is methyl, and in another aspect, it is F; in one aspect of these embodiments, R2 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 containing at least two 1,4-phenylene moieties (700) has structure (II); in one aspect of this embodiment, R1 is H, in another aspect, it is methyl, and in another aspect, it is F; in one aspect of these embodiments, R2 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 containing at least two 1,4-phenylene moieties (700) has structure (IIa); in one aspect of this embodiment, R1 is H, in another aspect, it is methyl, and in another aspect, it is F; in one aspect of these embodiments, R2 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 containing at least two 1,4-phenylene moieties (700) has structure (III); in one aspect of this embodiment, R1 is H, in another aspect, it is methyl, and in another aspect, it is F; in one aspect of these embodiments, R2 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 containing at least two 1,4-phenylene moieties (700) has structure (IV); in one aspect of this embodiment, R1 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 containing at least two 1,4-phenylene moieties (700) has structure (V). In another aspect of this embodiment, the linear organic liquid crystal core structure containing at least two 1,4-phenylene moieties (700) has structure (VI). In another aspect of this embodiment, the linear organic liquid crystal core structure containing at least two 1,4-phenylene moieties (700) has structure (VI). In another aspect of this embodiment, the linear organic liquid crystal core structure containing at least two 1,4-phenylene moieties (700) has structure (VII).In another aspect of this embodiment, the linear organic liquid crystal core structure containing at least two 1,4-phenylene moieties (700) has structure (VIII).

[0079]

[0080]

[0081] In another aspect of the above composition, in the liquid crystal compound (300), the polar graft group (800) is selected from structure (Ip), structure (Ipa), structure (IIp), and structure (IIpa), where L1 and L2 are each independently selected from C-2 to C-4 linear alkylene spacer groups, and *** is the attachment point of the polar anchoring group to the liquid crystal compound. In another aspect of this embodiment, the polar graft group (800) has structure (Ip), in another aspect, it has structure (Ipa), in another aspect, it has structure (IIp), and in another aspect, it has structure (IIpa). In one aspect of the embodiment having structure (Ip), L1 is a C-2 linear alkylene, in another aspect, it is a C-3 linear group, and in another aspect, it is a C-4 linear alkylene. In one aspect of the embodiment having structure (Ipa), L1 is a C-2 linear alkylene, in another aspect, it is a C-3 linear group, and in another aspect, it is a C-4 linear alkylene. In one aspect of the embodiment having structure (IIp), L2 is a C-2 linear alkylene, in another aspect, it is a C-3 linear group, and in another aspect, it is a C-4 linear alkylene. In one aspect of the embodiment having structure (IIpa), L2 is a C-2 linear alkylene, in another aspect, it is a C-3 linear group, and in another aspect, it is a C-4 linear alkylene.

[0082]

[0083] In another aspect of the above composition, in the liquid crystal compound (300), the polar graft group (800) is selected from structure (IIIp), structure (IVp), structure (Vp), structure (VIp), structure (VIIp), structure (VIIIp), and structure (IXp), where L3, L4, L5, L6, and L7 are each independently selected from C-2 to C-4 linear alkylene spacer groups, *** is the attachment point of the polar anchoring group to the liquid crystal compound, R p1 is C-1 to C-4 alkoxy, and R p2is a C-1 to C-4 alkyl or a C-1 to C-4 alkoxy. In one aspect of this embodiment, the polar graft group has the structure (IIIp). In another aspect of this embodiment, L3 is a C-2 straight-chain alkylene group. In another aspect, L3 is a C-3 straight-chain alkylene group. In another aspect, it is a C-4 straight-chain alkylene group. In one aspect of this embodiment, the polar graft group has the structure (IVp). In one aspect of this embodiment, L4 is a C-2 straight-chain alkylene group. In another aspect, L4 is a C-3 straight-chain alkylene group. In another aspect, it is a C-4 straight-chain alkylene group. In one aspect of this embodiment, the polar graft group has the structure (Vp). In one aspect of this embodiment, Rp1 is methoxy. In another aspect, it is ethoxy. In another aspect, it is n-propoxy. In another aspect, it is n-butoxy. In one aspect of this embodiment, Rp2 is methyl. In another aspect, it is ethyl. In another aspect, it is n-propyl. In another aspect, it is n-butyl. In another aspect of this embodiment, Rp2 is methoxy. In another aspect, it is ethoxy. In another aspect, it is n-propoxy. In another aspect, it is n-butoxy. In one aspect of this embodiment, the polar graft group has the structure (VIp). In one aspect of this embodiment, Rp1 is methoxy. In another aspect, it is ethoxy. In another aspect, it is n-propoxy. In another aspect, it is n-butoxy. In one aspect of this embodiment, Rp2 is methyl. In another aspect, it is ethyl. In another aspect, it is n-propyl. In another aspect, it is n-butyl. In another aspect of this embodiment, Rp2 is methoxy. In another aspect, it is ethoxy. In another aspect, it is n-propoxy. In another aspect, it is n-butoxy. In another aspect of this embodiment, the polar graft group has the structure (VIIp). In another aspect of this embodiment, the polar graft group has the structure (VIIIp). In one aspect of this embodiment, L6 is a C-2 straight-chain alkylene group. In another aspect, it is a C-3 straight-chain alkylene group. In another aspect, it is a C-4 straight-chain alkylene group. In another aspect of this embodiment, the polar graft group has the structure (IXp). In one aspect of this embodiment, L7 is a C-2 straight-chain alkylene group. In another aspect, it is a C-3 straight-chain alkylene group. In another aspect, it is a C-4 straight-chain alkylene group.

[0084]

[0085] In another aspect of the above composition, the liquid crystal compound (300) is selected from compounds having structures (M1), (M2), (M3), (M4), (M5), and (M7). In one aspect of this embodiment, it has structure (M1), in another aspect, it has structure (M2), in another aspect, it has structure (M3), in another aspect, it has structure (M4), in another aspect, it has structure (M5), and in another aspect, it has structure (M7).

[0086]

[0087] In another aspect of the above composition, the liquid crystal compound (300) is selected from compounds having structures (M8), (M9), (M10), (M11), (M12), (M13), and (M14). In one aspect of this embodiment, it has structure (M8), in another aspect, it has structure (M10), in another aspect, it has structure (M11), in another aspect, it has structure (M12), in another aspect, it has structure (M13), and in another aspect, it has structure (M14).

[0088]

[0089] In another aspect of the above composition, the liquid crystal compound (300) is a compound having structure (M4),

[0090]

[0091] In another aspect of the above composition, the liquid crystal compound (300) is selected from compounds 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).

[0092]

[0093] In another aspect of the above composition, the liquid crystal compound (300) is selected from compounds having structures (M10) and (M11). In one aspect of this embodiment, it has structure (M10), and in another aspect, it has structure (M11).

[0094]

[0095] In another aspect of the above, the liquid crystal compound is present in the organic spin-coating solvent at a loading of from about 0.5 wt.% to about 2.0 wt.%.

[0096] In another aspect of the above composition, the organic spin-coating solvent is a single organic solvent or a mixture of at least two organic solvents selected from the group consisting of: 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, or diethylene glycol dimethyl ether; glycol ether ester derivatives such as ethyl cellosolve acetate, methyl cellosolve acetate, or propylene glycol monomethyl ether acetate (PGMEA); carboxylates of monocarboxylic acids selected from ethyl acetate, n-butyl acetate, and amyl acetate; carboxylates of dicarboxylic acids selected from diethyl oxalate and diethyl malonate; dicarboxylates of diols selected from ethylene glycol diacetate and propylene glycol diacetate; hydroxycarboxylates selected from methyl lactate, ethyl lactate (EL), ethyl glycolate, and ethyl 3-hydroxypropionate; keto esters selected from methyl pyruvate and ethyl pyruvate; alkoxycarboxylates 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; ketol derivatives selected from acetol and diacetone alcohol; ketals or acetals selected from 1,3-dioxolane and diethoxypropane, butyrolactone; amides selected from dimethylacetamide and dimethylformamide, and anisole.

[0097] In another aspect of the above composition, the organic spin-coating solvent is a mixture of PGME and PGMEA. In one aspect of this embodiment, it is from about 50 wt.% PGME to about 80 wt.% PGMEA and from about 20 wt.% PGMEA to about 80 wt.% PGMEA. In one aspect of this embodiment, it is about 70 wt.% PGME and about 30 wt.% PGMEA.

[0098] In another aspect of the above composition, they may additionally contain a surfactant as an additive to facilitate coating.

[0099] A method of using the composition of the present invention.

[0100] Another aspect of the present invention is a method for selectively forming a self-assembled monolayer (SAM) of liquid crystal (LC) on a non-metallic region in a hybrid substrate comprising both metal and non-metallic regions, the method comprising the steps of:

[0101] i) Spin-coat any of the compositions as described on a hybrid substrate, wherein the liquid crystal has a polar anchoring group (800) that is an alkyl-polyol coordination moiety or a moiety containing at least one alkylene hydroxyl as described herein, wherein the non-metal region is selected from silicon dioxide, silicon with native oxide, silicon nitride, and silicon oxynitride, and the metal region is selected from tungsten, gold, silver, copper, cobalt, ruthenium, zirconium, titanium, and hafnium,

[0102] ii) Bake at a temperature ranging from about 150 °C to about 180 °C for about 2 min to about 10 min under an inert gas,

[0103] iii) Rinse with an organic spin-coating solvent,

[0104] iv) Air-dry the substrate,

[0105] v) Repeat steps i) to iv) twice to obtain a self-assembled monolayer of liquid crystal on both the metal and non-metal regions,

[0106] vi) Rinse the substrate with a dilute aqueous solution of an acid to selectively remove the self-assembled monolayer of liquid crystal on the metal region,

[0107] vii) Rinse the substrate with water and air-dry to obtain a substrate in which only the non-metal region has a SAM of LC.

[0108] "Repeating steps i) to iv) twice" in step v) means that the method includes at least three completions of steps i) to iv) in total.

[0109] In one aspect of the method, the liquid crystal is a liquid crystal in which the polar graft group is an alkyl-polyol coordination moiety or a moiety containing at least one alkylene hydroxyl group, and is selected from structure (Ip), structure (Ipa), structure (IIp), and structure (IIpa), where L1 and L2 are each independently selected from C-2 to C-4 straight-chain alkylene spacers, and *** is the attachment point of the polar anchoring group to the liquid crystal compound. In another aspect of this embodiment, the polar graft group (800) has structure (Ip), in another aspect, it has structure (Ipa), in another aspect, it has structure (IIp), and in another aspect, it has structure (IIpa). In one aspect of the embodiment having structure (Ip), L1 is a C-2 straight-chain alkylene, in another aspect, it is a C-3 straight-chain group, and in another aspect, it is a C-4 straight-chain alkylene. In one aspect of the embodiment having structure (Ipa), L1 is a C-2 straight-chain alkylene, in another aspect, it is a C-3 straight-chain group, and in another aspect, it is a C-4 straight-chain alkylene. In one aspect of the embodiment having structure (IIp), L2 is a C-2 straight-chain alkylene, in another aspect, it is a C-3 straight-chain group, and in another aspect, it is a C-4 straight-chain alkylene. In one aspect of the embodiment having structure (IIpa), L2 is a C-2 straight-chain alkylene, in another aspect, it is a C-3 straight-chain group, and in another aspect, it is a C-4 straight-chain alkylene.

[0110]

[0111] In another aspect of the method, the liquid crystal is selected from liquid crystals having structures (M1), (M2), (M3), (M4), (M5), and (M7). In a more specific embodiment, the liquid crystal has structure (M1), in another aspect, it has structure (M2), in another aspect, it has structure (M3), in another aspect, it has structure (M4), in another aspect, it has structure (M5), and in another aspect, it has structure (M7).

[0112] Another aspect of the present invention is a method for selectively atomic layer depositing on a metal region of a hybrid substrate comprising both metal and non-metal regions, the method comprising the following steps:

[0113] ia) Prepare a hybrid substrate, wherein the non-metal region has a self-assembled monolayer of a liquid crystal according to the above method, the method using any one of the compositions described herein, wherein the liquid crystal has a polar anchoring group (800) that is an alkyl-polyol coordination moiety or at least one alkylene hydroxyl group,

[0114] iia) Use atomic layer deposition techniques to more selectively deposit a metal oxide on the metal region that does not have a self-assembled monolayer of the liquid crystal.

[0115] In a more specific aspect of the method, the polar anchoring group (800) is selected from structures (Ip), (Ipa), (IIp), and (IIpa) as described herein.

[0116] In a more specific aspect of the method, the liquid crystal is a liquid crystal having structures (M1), (M3), (M4), (M5), or (M7) as 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).

[0117] In a more specific embodiment of the method, the atomic layer deposition technique is a technique of deposition using from about 10 to about 50 deposition cycles, where each cycle employs the following treatments at a temperature from about 250 °C to about 350 °C: treatment with (MeCp)2Hf(OMe)Me vapor for about 1 to about 5 s; subsequent treatment with N2 for about 5 s to about 15 s; treatment with H2O for about 1 s to about 5 s; and treatment with N2 for about 5 s to about 15 s.

[0118] Another aspect of the present invention is a method for selectively forming a self-assembled monolayer (SAM) of liquid crystal (LC) on a metal region in a hybrid substrate containing both metal and non-metal regions, the method comprising the following steps:

[0119] ib) Spin-coating any one of the described compositions on the hybrid substrate, wherein the liquid crystal has a polar anchoring group (800) selected from a moiety containing phosphonate, a moiety containing phosphonic acid, a moiety containing thiol, a moiety containing amino, and wherein further the non-metal region is selected from silicon dioxide, silicon with native oxide, silicon nitride, and silicon oxynitride, and the metal region is selected from tungsten, gold, silver, copper, cobalt, ruthenium, zirconium, titanium, and hafnium.

[0120] iib) Bake at a temperature ranging from about 150 °C to about 180 °C for about 2 min to about 10 min under an inert gas,

[0121] iiib) Rinse with an organic spin-coating solvent,

[0122] ivb) Air-dry the substrate,

[0123] vb) Repeat steps ib) to ivb) twice,

[0124] vib) Air-dry the substrate to obtain a self-assembled monolayer of liquid crystal only on the metal region of the substrate.

[0125] In another aspect of the method, the polar group (800) is selected from groups having structure (IIIp), structure (IVp), structure (Vp), structure (VIp), structure (VIIp), structure (VIIIp), and structure (IXp), as described herein.

[0126] In another aspect of the method, the liquid crystal is selected from liquid crystals having structures (M8), (M9), (M10), (M11), (M12), (M13), and (M14), as described herein. In a more specific embodiment c, the liquid crystal has structure (M1), in another aspect, it has structure (M8), in another aspect, it has structure (M9), in another aspect, it has structure (M10), in another aspect, it has structure (M11), in another aspect, it has structure (M12), in another aspect, it has structure (M13), and in another aspect, it has structure (M14).

[0127] Another aspect of the present invention is a method for selectively atomic layer depositing on a metal region of a hybrid substrate comprising both metal and non-metal regions, the method comprising the steps of:

[0128] ic) preparing a hybrid substrate, wherein the metal region has a self-assembled monolayer of a liquid crystal according to the method above, the method using any one of the compositions as described herein, wherein the liquid crystal has a polar anchoring group (800) selected from groups having structure (IIIp), structure (IVp), structure (Vp), as described herein, (or any one of the compositions containing more specific liquid crystals of the type discussed above),

[0129] iic) using atomic layer deposition techniques to more selectively deposit a metal oxide on the non-metal region that does not have a self-assembled monolayer of the liquid crystal.

[0130] In a more specific aspect of this embodiment, the atomic layer deposition technique is a technique that uses about 10 to about 50 deposition cycles, wherein each cycle uses the following treatments at a temperature of about 250 °C to about 350 °C: treatment with (MeCp)2Hf(OMe)Me vapor for about 1 to about 5 s; subsequent treatment with N2 for about 5 s to about 15 s; treatment with H2O for about 1 s to about 5 s; and treatment with N2 for about 5 s to about 15 s. Examples

[0131] Reference will now be made to more specific embodiments of the present disclosure and experimental results that support these embodiments. Examples are given below to more fully illustrate the disclosed subject matter and should not be construed as limiting the disclosed subject matter in any way.

[0132] It will be apparent to those skilled in the art that various modifications and variations can be made to the disclosed subject matter and the specific embodiments provided herein without departing from the spirit or scope of the disclosed subject matter. Accordingly, it is intended that the disclosed subject matter, including the description provided by the following embodiments, cover modifications and variations of the disclosed subject matter that fall within the scope of any claim and its equivalents.

[0133] Although the disclosed and claimed subject matter has been described and illustrated to a certain degree of particularity, it is to be understood that the disclosure is by way of example only and that many variations in the conditions and order of steps can be resorted to by those skilled in the art without departing from the spirit and scope of the disclosed and claimed subject matter.

[0134] Chemical

[0135] Unless otherwise stated, all chemicals were purchased from Sigma Aldrich (3050 Spruce St., St. Louis, MO 63103).

[0136] Instrument

[0137] Ellipsometry

[0138] Ellipsometry thickness measurements were performed using J.A. Woollam. SAM FT was measured using a single layer model with an RI of 1.45 for the organic layer.

[0139] X-ray photoelectron spectroscopy (XPS) measurements

[0140] These were performed using a K-alpha from Thermo-Fisher. The experiments were run using a pass energy of 50 eV, a step size of 0.100 eV, a dwell time of 50 ms, and 10 scans / element.

[0141] Water contact angle (WCA) measurements

[0142] These were performed at room temperature using a dynamic contact angle measurement tool from Kruss. A 4 μL deionized water droplet was used. The reported values are the average of measurements at 5 - 6 points per 1 × 1 inch specimen.

[0143] DSC measurements

[0144] DSC measurements of the glass transition temperature were performed using a TA Instruments DSC 2500 under nitrogen with a ramp of 10 °C / min during heating and cooling cycles. The glass transition temperature (T g)Measured during the first heating scan from 0 °C to 300 °C. Consider the midpoint of the endothermic transition. In the characterization of liquid crystal compounds by DSC, the following abbreviations are used to denote different types of liquid crystal physical transitions: T g = glass transition, N = nematic transition, Sm = smectic transition, SmA = smectic A transition, SmB = smectic B transition, SmC = smectic C transition. I = isotropic phase transition.

[0145] 1 1H NMR

[0146] Recorded in CDCl3 using a Bruker Advanced III 400 MHz spectrometer 1 1H NMR spectra.

[0147] Si / SiOx wafers

[0148] Six-inch and eight-inch wafers were obtained from Silicon Valley Microelectronics (SVM).

[0149] X-ray reflectivity (XRR) measurements.

[0150] These measurements were carried out at the Darmstadt Technical University, Germany.

[0151] 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-μm filter. Using a three-step spin-coat-bake-rinse protocol, SAMs were prepared on substrates SiOx, copper, tungsten, cobalt, and ruthenium as follows: The solution was spin-coated at 1500 rpm and baked at 170 °C under nitrogen for 5 min, rinsed with excess EBR, blown dry, and used for further analysis. SAMs were prepared on SiOx using SMLs with hydroxyl anchoring groups. The theoretical and experimental film thicknesses (ellipsometry, VASE) and WCAs of a series of SAMs are listed in Table 1. As can be seen from the table, the film thickness values are higher than the theoretical values, while the WCA values are higher than 90°, indicating a hydrophobic surface due to the non-polar alkyl tail groups. The film thickness and molecular density were analyzed and calculated using X-ray reflectometry. As shown in Table 2, the XRR FT values are lower than those of ellipsometry. In addition, per nm 2The value of the molecule indicates a medium packing density. Due to the medium packing density, the SAM molecule exhibits relatively medium thermal stability, and TGA shows that the SAM starts to degrade above 270 °C. At 300 °C, the passivation characteristics for ALD of hafnium oxide were measured using MeCp)2Hf(OMe)Me(2s), N2(10s), H2O(2s), N2(10s) / cycle. The SML200-series SAM shows passivation up to 50 cycles for ALD of HfOx. Due to the medium SAM packing density, medium passivation was obtained. The comparison of monofunctional hydroxyl groups with bifunctional hydroxyl groups indicates that bifunctional hydroxyl groups are required to obtain good SAM packing density.

[0152] The formulations SML-301, SML-302, SML-402 to SML-407, SML351-SML-352 with thiol, amino, and diethyl phosphonate anchoring groups (using LCCs of structures (M8), (M9), (M12), (M17), (M10), (M11) respectively) were used for selective SAM deposition on metal surfaces. The SAM was prepared at a baking 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), (M14) respectively) on metal vs. SiOx. Figure 6 Shows the ALD passivation of SML-302 and SML-404 (structures (M9), (M14) respectively) on copper, tungsten, and SiOx. The passivation data indicate that the SAM packing density follows the reactivity order of thiol > amino > diethyl phosphonate. Copper shows a better packing density than tungsten. The SAM packing density reflects the passivation characteristics for ALD of HfOx. Due to the medium thermal stability of the SAM, the passivation characteristics were measured at 200 °C. The passivation of SML-302, SML-404, and SML-406 (made from LLCs of structures (M9), (M14), and (M16) respectively) on copper corresponds to ~6 nm of HfOx. The passivation characteristics of SML-406 (M16) on different metals were compared, which shows Co > Cu > W > Ru, indicating the corresponding SAM packing density. The FT measured and reported in Table 1-3 was measured using ellipsometry (VASE). The TGA analysis reported herein was performed at a heating rate of 10 °C / min. The water contact angle (WCA) was also measured.

[0153]

[0154]

[0155] Table 1 SAM characteristics on LCC formulations and SiOx

[0156]

[0157] The FT measured and reported in Table 1 was measured using ellipsometry (VASE). TGA analysis was performed using a heating rate of 10 °C / min, and the water contact angle (WCA)

[0158] Table 2 Tabulated values from XRR analysis

[0159]

[0160] Figure 4 Shows the relative stability of the SAMs measured via the change in the water contact angle (WCA) as a function of increasing temperature. These materials were heated for 5 minutes under nitrogen at each of the different temperatures indicated in the figure. From these measurements, they have the following order of thermal stability: SML-204 > SML-207 > SML-202 > SML-201 > SML-205 > SML-203. All SAMs show good stability up to 250 °C. The relative LC-SAM stability depends on the LC-SAM stacking order (ring substitution) and the type of anchoring group. For example, both SML-205 and SML-207 have 1,2 vicinal diols, but the C2 spacer in SML-207 shows better stability than SML-205 with a C3 spacer. SML-204 has two single alcohol groups that form two chemical bonds via two separate spacer groups and has better thermal stability than SML-207. Both SML-203 and SML-207 have vicinal diols and a C3 spacer, but SML-203 has ethyl and fluorine groups on the aromatic ring, thus reducing the LC-packing density due to steric hindrance.

[0161] Figure 5 Shows the relative stability of the SAMs containing the hydroxyl moiety of the polar anchoring group measured via the change in the percentage of carbon atoms in XPS after heating these SAMs under nitrogen at different temperatures for 5 min. XPS analysis shows the relative C atom % (at. %) percentage values. SML-205 and SML-207 show higher C at. % due to their molecular composition having a higher carbon content. At 250 °C, the relative change in C at. % is very small for all SAMs because after the surface chemical bonds are broken, the SAM still remains on the surface and contributes to the total C at. %.

[0162] Figure 6Shows the results of a study on the passivation characteristics of a dielectric SAM for atomic layer deposition of hafnium oxide on SML-201 to SML-207 at 300 °C. From this study, it was found that after 100 cycles, the maximum resistance to hafnium oxide deposition was SML-205 (M5), followed by SML-204 (M4), SML-207 (M7), SML-202 (M2), and SML-201 (M1).

[0163] Table 3 shows the water contact angle studies conducted to measure the extent of SAM formation on metal substrates W and Cu compared to that on Si with native oxide. In this study, three SAM materials, SML-302 (M9), SML-352 (M11), and SML-404 (M14), which have thiol, diethyl phosphonate, or amino anchoring groups respectively, were compared. From this, it was seen that the functional group selectively reacts with the metal surface relative to SiOx.

[0164] Figure 7 Shows the results of XPS studies conducted on Si, W, and Cu substrates, which indicate that the normalized Cat.% is higher for both W and Cu, while it is very low for Si. It is demonstrated that the SAM selectively grafts onto the metal surface in the order of Cu >> W >>>> Si.

[0165] Table 3 Selective Examples: SAM Deposition on Metal Surfaces

[0166]

[0167] Figure 8 Shows the results of passivation, which was carried out to show the relative passivation characteristics of SML-302 and SML-404 for ALD of HfOx at 200 °C after 100, 200, and 300 cycles. This study shows that SML 404 shows better passivation relative to SML-302. Additionally, the order of passivation is Cu >> W >>>> Si.

[0168] Table 4 shows the results of water contact experiments conducted to determine the selectivity of SML-406 (M16) with amino anchor points on different metal substrates. The results show that the relative order of WCA is Ru > W > Cu >>> Si.

[0169] Figure 9 Shows the passivation of LC-SAM, SML-406 for atomic layer deposition of HFOx on various metals W, Cu, Co, Ru at 200 °C. These show that the relative order of passivation is Co > Cu >> W >>> Ru >>>> Si.

[0170] Table 4 Selective Deposition of SML-406 M16

[0171]

[0172] Synthesis of LCC SAM precursor

[0173] Preparation of the LCC (SML-201) of Structure (M1)

[0174] Step 3 in the Synthesis of the LLC of Structure (M1)

[0175] Scheme 1 shows an overview of Step 3 in the synthesis of the LCC of Structure (M1). Specifically, a solution of 2-[2-[3-ethyl-4-[4-(4-pentylcyclohexyl)phenyl]phenyl]ethyl]-malonic acid ester (17.86 g, 34.29 mmol) in THF (75 mL) was added dropwise to LiAlH4 (1.90 g, 50.06 mmol) in toluene (15 mL). The mixture was stirred at 65 °C for 1 h, and then 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 Na2SO4, filtered off, and the solvent was removed under reduced pressure. Further purification by column chromatography (silica gel, heptane / ethyl acetate: 1 / 4) gave 2-[2-[3-ethyl-4-[4-(4-pentylcyclohexyl)phenyl]phenyl]ethyl]-diethyl malonate (11.0 g, 25.19 mmol, HPLC: 99.4%) as a colorless solid in a yield of 73%. 1 1H-NMR (CDCl3, 500 MHz): 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 = 7.5 Hz, 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 = 12.8 Hz, J = 3.3 Hz, 2H), 1.36 - 1.20 (m, 9H), 1.10 (t, J = 7.5 Hz, 3H), 1.09 - 1.07 (m, 1H), 0.90 (t, J = 7.0 Hz, 3H). APCI-MS: m / z: 437.3. DSC: T g -67 °C, 79 °C Sm, 112 °C SmA, 122 °C I. TGA: T 5％损失 = 303 °C.

[0176]

[0177] Scheme 1

[0178] Preparation of LCC (SML-201) of Structure (M1)

[0179] Step 3 in the Synthesis of LCC of Structure (M1)

[0180] Scheme 2 shows a general overview of the second step in the synthesis of LCC of Structure (M1). Specifically, diethyl malonate (6.4 mL, 0.042 mol) and ethyl 2-[3-ethyl-4-[4-(4-pentylcyclohexyl)phenyl]phenyl]methanesulfonate (9.6 g, 0.021 mol) were added to a solution of sodium ethoxide (2.8 g, 0.042 mol) in ethanol (30 mL), and the mixture was stirred overnight at 75 °C. The mixture was allowed to cool to room temperature, and then water was added. The aqueous phase was extracted with MTBE, and the combined organic phases were dried over Na2SO4, filtered off, 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]malonate (11.8 g, 0.011 mol, HPLC: 99.0%) as a colorless oil, with a yield of 53%.

[0181] 1 1H-NMR (CDCl3, 500 MHz): 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 = 7.5 Hz, 2H), 2.68 (dd, J = 8.9 Hz, J = 6.7 Hz, 2H), 2.58 (q, J = 7.5 Hz, 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 = 7.5 Hz, 3H), 1.09 - 1.07 (m, 1H), 0.90 (t, J = 7.5 Hz, 3H). EI-MS: m / z: 520.4.

[0182]

[0183] Scheme 2

[0184] Step 2 in the Synthesis of LCC of Structure (M1)

[0185] Scheme 3 shows a general overview of the second step in the synthesis of the 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). At 0 °C, methanesulfonyl chloride (8.3 mL, 107.5 mmol) was added, and the resulting solution was stirred overnight at room temperature. The mixture was diluted with water and the aqueous phase was extracted with dichloromethane, and 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 ethyl 2-[3-ethyl-4-[4-(4-pentylcyclohexyl)phenyl]phenyl]methanesulfonate (13.3 g, 29.0 mmol, HPLC: 99.3%) as a colorless solid in 81% yield.

[0186]

[0187] Scheme 3

[0188] Step 1 in the synthesis of the LCC of structure (M1)

[0189] Scheme 4 shows a general overview of the first step in the synthesis of the 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 in Yano, Kyoichi et al., JP 2017025007) in THF (180 mL) was added, and the mixture was stirred at 70 °C for 3 h. 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 min. The mixture was diluted with THF (200 mL) and stirred overnight at room temperature. 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 off, 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%).

[0190]

[0191] Scheme 4

[0192] Preparation of LCC (SML-202) of Structure (M2)

[0193] Step 4 in the Synthesis of LCC of Structure (M2)

[0194] Scheme 5 shows a general overview of the fourth step in the synthesis of LCC of Structure (M2). Specifically, a solution of diethyl 2-[2-(2-fluoro-4'-propyl-biphenyl-4-yl)-ethyl]-malonate (4.80 g, 11.20 mmol) in THF (20 mL) was added dropwise to LiAlH4 (0.55 g, 14.49 mmol) in toluene (4 mL). The mixture was stirred at 65 °C for 1 h, then 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 Na2SO4, filtered off, 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 (1.70 g, 5.37 mmol, HPLC: 99.6%) as a colorless solid in a yield of 45%. 1 1H-NMR (DMSO-d6, 400 MHz): δ = 7.46 - 7.37 (m, 3H), 7.28 (d, J = 8.1 Hz, 2H), 7.15 - 7.09 (m, 2H), 4.43 (t, J = 5.2 Hz, 2H), 2.66 (dd, J = 9.2 Hz, J = 6.6 Hz, 2H), 2.59 (t, J = 7.6 Hz, 2H), 1.69 - 1.47 (m, 5H), 0.92 (t, J = 7.3 Hz, 3H). EI-MS: m / z: 316.1. DSC: 66 °C SmC, 73 °C I. TGA: T 5％损失 = 258 °C.

[0195]

[0196] Scheme 5

[0197] Preparation of LCC (SML-202) of Structure (M2)

[0198] Step 3 in the Synthesis of LLC of Structure (M2)

[0199] Scheme 6 shows a general overview of the third step in the synthesis of the LCC of structure (M2). Specifically, diethyl malonate (6.4 mL, 0.06 mol) and sodium ethoxide (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 Na2SO4, filtered off, 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]-diethyl malonate (4.8 g, 0.01 mol, GC: 99.7%) as a colorless oil, with a yield of 40%.

[0200] 1 1H-NMR (CDCl3, 500 MHz): δ = 7.45 (dq, J = 8.4 Hz, J = 2.1 Hz, 2H), 7.38 (t, J = 8.0 Hz, 1H), 7.24 (d, J = 8.2 Hz, 2H), 7.02 (dd, J = 7.8 Hz, J = 1.7 Hz, 1H), 6.98 (dd, J = 11.6 Hz, J = 1.7 Hz, 1H), 4.24 - 4.15 (m, 7H), 2.69 (dd, J = 8.8 Hz, J = 6.5 Hz, 2H), 2.62 (dd, J = 8.6 Hz, J = 6.8 Hz, 2H), 1.72 - 1.62 (m, 2H), 1.28 (t, J = 7.2 Hz, 6H), 0.97 (t, J = 7.3 Hz, 3H). EI-MS: m / z: 400.2.

[0201]

[0202] Scheme 6

[0203] Step 2 in the synthesis of the LCC of structure (M2)

[0204] Scheme 7 shows a general overview of the second step in the synthesis of the 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) with a yield of 69%.

[0205]

[0206] Scheme 7

[0207] Step 1 in the synthesis of the LCC of structure (M2)

[0208] Scheme 8 shows a general overview of the first step in the synthesis of the LCC of structure (M2). Specifically, at -78 °C, 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), and the mixture was stirred for an additional 30 min at this temperature. At -78 °C, ethylene oxide (5.17 mL, 0.11 mol) was added. After stirring for 1 h at -78 °C, BF3·Et2O (27.90 mL, 0.11 mol, 48%) was added over 1 h. The solution was now 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 off, 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. 1 1H-NMR (CDCl3, 500 MHz): δ = 7.46 (dq, J = 8.4 Hz, J = 2.1 Hz, 2H), 7.38 (t, J = 8.0 Hz, 1H), 7.26 (d, J = 8.2 Hz, 2H), 7.07 (dd, J = 7.8 Hz, J = 1.8 Hz, 1H), 7.04 (dd, J = 11.5 Hz, J = 1.7 Hz, 1H), 3.91 (q, J = 6.4 Hz, 2H), 2.90 (t, J = 6.5 Hz, 2H), 2.63 (dd, J = 8.6 Hz, J = 6.8 Hz, 2H), 1.76 - 1.62 (m, 2H), 1.51 (t, J = 5.8 Hz, 1H), 0.98 (t, J = 7.3 Hz, 3H). EI-MS: m / z: 258.0

[0209]

[0210] Scheme 8

[0211] Preparation of the LCC (SML-203) of structure (M3)

[0212] The LCC of structure (M3) (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., WO 2014 / 094959A1.

[0213]

[0214] Preparation of the LCC (SML-204) of structure (M4)

[0215]

[0216] Step 3 in the synthesis of the LCC of structure (M4)

[0217] In the third step of 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 h, then 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 (3.30 g, 9.55 mmol, HPLC: 99.7%) as a colorless solid in 65% yield.

[0218] 1 1H-NMR (CDCl3, 500 MHz): δ = 7.45 (d, J = 8.2 Hz, 2H), 7.22 (d, J = 8.2 Hz, 2H), 7.21 - 7.12 (m, 2H), 6.99 (d, J = 8.3 Hz, 1H), 4.43 (td, J = 6.1 Hz, J = 2.0 Hz, 2H), 4.16 - 4.12 (m, 4H), 3.92 - 3.89 (m, 4H), 2.62 (t, J = 7.7 Hz, 2H), 1.69 - 1.60 (m, 2H), 1.41 - 1.28 (m, 4H), 0.90 (t, J = 7.0 Hz, 3H). EI-MS: m / z: 344.1. DSC: 128 °C I. TGA: T 5％损失 = 273 °C.

[0219] Step 2 in the synthesis of the LCC of structure (M4)

[0220] Scheme 9 shows a general overview of the second step in the synthesis of the 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 BNaO2·4H2O (5.73 g, 0.04 mol) in water (40 mL). Pd(PPh3)2Cl2 (1.04 g, 1.45 mmol) and THF (150 mL), and the mixture was stirred at 70 °C overnight. The mixture was allowed to cool to room temperature and then water was added. The aqueous phase was extracted with ethyl acetate, and the combined organic phases were dried over Na2SO4, filtered off, 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 (8.70 g, 15.03 mmol, HPLC: 99.0%) as a colorless oil in 58% yield. EI-MS: m / z: 572.4.

[0221]

[0222] Scheme 9

[0223] Step 2 in the synthesis of the LCC of structure (M4)

[0224] Scheme 10 shows a general overview of the first step in the synthesis of the 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, and then (2-bromoethoxy)(tert-butyl)dimethylsilane dissolved in DMF (30 mL) was added. After stirring at room temperature for 3 days, the reaction mixture was poured into water, acidified with 2N 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 (18.2 g, 35.27 mmol, GC: 98%) as a colorless oil in 67% yield. 11H-NMR (CDCl3, 500 MHz): δ = 6.95 (d, J = 2.3 Hz, 1H), 6.90 (dd, J = 8.5, 2.3 Hz, 1H), 6.69 (d, J = 8.5 Hz, 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).

[0225]

[0226] Scheme 10

[0227] Synthesis of LCC (SML - 205) of structure (M5)

[0228]

[0229] Using appropriate reagents, the LCC of structure (M5) was prepared using the general procedure employed for the LCC of structure (M3). 1 1H-NMR (DMSO-d6, 500 MHz): δ = 7.19 - 7.04 (m, 8H), 4.27 (t, J = 5.1 Hz, 2H), 3.43 - 3.30 (m, 4H), 2.80 (s, 4H), 2.52 - 2.50 (m, 5H), 2.41 (tt, J = 12.0 Hz, J = 3.3 Hz, 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, 3.7 Hz, 2H), 0.89 (t, J = 7.3 Hz, 3H). EI-MS: m / z: 422.3. DSC: 155 °C I.

[0230] Synthesis of LCC (SML - 207) of structure (M7)

[0231]

[0232] Using appropriate reagents, the LCC of structure (M5) was prepared using the general procedure employed for the LCC of structure (M3). 11H-NMR (CDCl3, 500 MHz): 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 = 12.2 Hz, J = 3.3 Hz, 1H), 2.14 (t, J = 5.1 Hz, 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 = 7.3 Hz, 3H). EI-MS: m / z: 408.3. DSC: 163 °C SmB, 173 °C SmA, 178 °C I.

[0233] Synthesis of LLC (SML-301) of Structure (M8)

[0234]

[0235] The LCC of Structure (M8) (2-[4-[4-(4-Ethylcyclohexyl)cyclohexyl]-2,3-difluoro-phenoxy]ethanethiol) is available and prepared according to the procedure of Yun, Yong-Kuk et al., WO 2017045740.

[0236] Synthesis of LCC (SML-302) of Structure (M9)

[0237] Step 3 in the Synthesis of Structure (M9)

[0238] Scheme 11 shows a general overview of the third step in the synthesis of the LCC of Structure (M9). Specifically, a suspension of S-{3-[2-Ethyl-4'-(4-pentyl-cyclohexyl)-biphenyl-4-yl]-propyl} thioacetate (12.4 g, 27.5 mmol) in methanol (500 mL) was cooled to 2 °C. Sodium methoxide (30% in methanol, 25 mL, 134.7 mmol) was added, and the reaction mixture was stirred at 0 °C for 1 h. After stirring for an additional 1 h at 15 °C, 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 Na2SO4 and filtered. Further purification by column chromatography (silica gel, chloro-butane / 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 (8.3 g, 20.3 mmol, HPLC: 99.7%) as a colorless oil in 74% yield. 11H-NMR (CDCl3, 500 MHz): δ = 7.26 - 7.22 (m, 4H), 7.16 - 7.12 (m, 2H), 7.06 (dd, J = 7.7 Hz, J = 1.9 Hz, 1H), 2.77 (t, J = 7.5 Hz, 2H), 2.62 (q, J = 7.5 Hz, 4H), 2.53 (tt, J = 12.1 Hz, J = 3.4 Hz, 1H), 2.05 - 1.95 (m, 4H), 1.94 - 1.90 (m, 2H), 1.57 - 1.46 (m, 2H), 1.42 - 1.23 (m, 11H), 1.13 (t, J = 7.5 Hz, 3H), 0.93 (t, J = 7.0 Hz, 3H). EI-MS: m / z: 408.3. DSC: Tg -64 °C, 22 °C N, (-33.8 °C) I. TGA: T 5％损失 = 294 °C.

[0239]

[0240] Scheme 11

[0241] Step 2 in the synthesis of the LCC of structure (M9)

[0242] Scheme 12 shows a general overview of the second step in the synthesis of the LCC of structure (M9). A solution of 3-[2-ethyl-4'-(4-pentyl-cyclohexyl)-biphenyl-4-yl]-propyl methanesulfonate (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 the mixture was 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 S-{3-[2-ethyl-4'-(4-pentyl-cyclohexyl)-biphenyl-4-yl]-propyl} thioacetate (12.5 g, 27.1 mmol, HPLC: 97.7%) as a slightly brown oil, with a yield of 68%.

[0243] 11H-NMR (CDCl3, 500 MHz): δ = 7.26 - 7.22 (m, 4H), 7.16 - 7.12 (m, 2H), 7.06 (dd, J = 7.7 Hz, J = 1.9 Hz, 1H), 2.96 (t, J = 7.3 Hz, 2H), 2.73 (dd, J = 8.6 Hz, J = 6.8 Hz, 2H), 2.61 (q, J = 7.5 Hz, 2H), 2.53 (tt, J = 12.2 Hz, J = 3.4 Hz, 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 = 7.5 Hz, 3H), 0.93 (t, J = 7.0 Hz, 3H).

[0244]

[0245] Scheme 12

[0246] Step 1 in the synthesis of the LCC of structure (M9)

[0247] Scheme 13 shows a general overview of the first step in the synthesis of the LCC of structure (M9),

[0248] 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 according to EP2883934] and 4-(dimethylamino)-pyridine (0.6 g, 4.91 mmol) in dichloromethane (200 mL). At 0 °C, methanesulfonyl chloride (4.3 mL, 55.5 mmol) was added, 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 for another 3 days at room temperature. The mixture was poured into dilute hydrochloric acid and stirred for 1 h at room temperature. 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 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%), with a yield of 72%. 11H-NMR (CDCl3, 500 MHz): δ = 7.26 - 7.22 (m, 4H), 7.16 - 7.12 (m, 2H), 7.06 (dd, J = 7.7 Hz, J = 1.9 Hz, 1H), 4.31 (t, J = 6.9 Hz, 2H), 3.04 (s, 1H), 2.80 (t, J = 7.5 Hz, 2H), 2.62 (q, J = 7.5 Hz, 2H), 2.57 - 2.48 (m, 1H), 2.18 - 2.12 (m, 2H), 1.99 - 1.90 (m, 6H), 1.57 - 1.44 (m, 4H), 1.38 - 1.24 (m, 8H), 1.13 (t, J = 7.6 Hz, 3H), 0.93 (t, J = 7.1 Hz, 3H).

[0249]

[0250] Scheme 13

[0251] Synthesis of LCC (SML - 351) of Structure (M10)

[0252] Step 2 in the Synthesis of LCC of Structure (M10)

[0253] Scheme 14 shows a general overview 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 h. The 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'-biphenyl]-4-yl]propyl]phosphonate (5.5 g, 0.01 mol, GC: 89%), with a yield of 38%.

[0254] 1 1H-NMR (CDCl3, 500 MHz): 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 = 7.6 Hz, 2H), 2.61 (q, J = 7.6 Hz, 2H), 2.53 (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 = 7.5 Hz, 3H), 0.93 (t, J = 7.0 Hz, 3H).

[0255]

[0256] Scheme 14

[0257] Step 1 in the synthesis of the LCC of structure (M10)

[0258] Scheme 15 shows a general overview of the second step in the synthesis of the LCC of structure (M10). Specifically, at 0 °C, 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 carbon tetrabromide (17.0 g, 5.8 mL, 0.05 mol) in THF (41 mL). 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) gave 4-(3-bromopropyl)-2-ethyl-4'-(4-pentylcyclohexyl)-1,1'-biphenyl (11.5 g, 0.02 mol, GC: 99.3%), with a yield of 98%.

[0259] 1 1H-NMR (DMSO-d6, 500 MHz): 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 = 7.0 Hz, 3H).

[0260]

[0261] Scheme 15

[0262] Synthesis of the LCC (SML-352) of structure (M11)

[0263] Scheme 16 shows a general overview of the second step in the synthesis of the LCC of structure (M11). Specifically, at -15 °C, 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 Et2O·BF3 (0.55 mmol, 56 μL) in 48 mL of anhydrous THF. 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 and stirred until all of 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)2 (167 mg, 0.12 mmol), P(OEt)3 (5.82 g, 3.50 mmol), and Cs2CO3 (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 provided 4-[4-(4-diethoxyphosphorylphenyl)-3-fluorophenyl]-2-fluoro-1-(4-propylphenyl)benzene (1.04 g, 0.20 mmol, GC: 96%) as a pale yellow solid in 28% yield. 1 1H-NMR (CDCl3, 500 MHz): δ = 7.96 - 7.92 (m, 2H), 7.75 - 7.73 (m, 2H), 7.59 - 7.43 (m, 8H), 7.32 (d, J = 8.2 Hz, 2H), 4.26 - 4.10 (m, 4H), 2.69 - 2.66 (m, 2H), 1.76 - 1.69 (m, 2H), 1.39 (t, J = 7.1 Hz, 6H), 1.02 (t, J = 7.3 Hz, 3H).

[0264]

[0265] Scheme 16

[0266] Synthesis of the LCC (SML-402) of structure (M12)

[0267] Scheme 17 shows a general overview of the second step in the synthesis of the 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[tricyclohexylphosphine]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 purity: 98.0%) as a colorless solid in a yield of 64%. 1 1H-NMR (CDCl3, 400 MHz): 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 = 7.5 Hz, 2H), 1.74 - 1.62 (m, 2H), 0.98 (t, J = 7.3 Hz, 3H). EI-MS: m / z: 323.1. DSC: 185 °C I. TGA: T 5％损失 = 247 °C.

[0268]

[0269] Scheme 17

[0270] Synthesis of the LCC (SML-403) of structure (M13)

[0271] Scheme 18 shows a general overview of the second step in the synthesis of the LCC of structure (M13). Specifically, 3,5-difluoro-4'-propyl-[1,1'-biphenyl]-4-yl-boronic acid (27.6 g, 0.10 mol), 4-bromo-aniline (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[tricyclohexylphosphine]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 purity: 99.1%) as a colorless solid in 31% yield. 1 1H-NMR (DMSO-d6, 300 MHz): δ = 7.68 (d, J = 8.2 Hz, 2H), 7.49 - 7.41 (m, 2H), 7.30 (d, J = 8.3 Hz, 2H), 7.16 - 7.12 (m, 2H), 6.70 - 6.62 (m, 2H), 5.34 (s, 2H), 2.60 (t, J = 7.5 Hz, 2H), 1.72 - 1.49 (m, 2H), 0.92 (t, J = 7.3 Hz, 3H). EI-MS: m / z: 323.1. DSC: 105 °C (99 °C) I. TGA: T 5％损失 = 239 °C.

[0272]

[0273] Scheme 18

[0274] Synthesis of the LCC (SML-404) of structure (M14)

[0275] Step 3 in the synthesis of the LCC of structure (M14)

[0276] Scheme 19 shows a general overview of the third step in the synthesis of the 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[tricyclohexylphosphine]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. In addition, the filtrate was 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 1H-NMR (CDCl3, 400 MHz): 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 = 8.5 Hz, J = 6.8 Hz, 2H), 1.77 - 1.62 (m, 2H), 0.99 (t, J = 7.3 Hz, 3H).

[0277] EI-MS: m / z: 399.2. DSC: 139 °C N, 315.2 °C I. TGA: T 5％损失 = 335 °C

[0278]

[0279] Scheme 19

[0280] Step 2 in the synthesis of the LCC of structure (M14)

[0281] Scheme 20 shows a general overview of the second step in the synthesis of the LCC of structure (M14). Specifically, at -95 °C, n-butyllithium (30 mL, 80.0 mmol, 2.7 M in heptane) was added dropwise to a solution of 1-fluoro-2-fluoro-4-[3-fluoro-4-(4-propylphenyl)phenyl]benzene (25.0 g, 64.6 mmol) in THF (970 mL). The reaction mixture was stirred at -95 °C for 2 h and then allowed to warm to -80 °C. The resulting solution was cooled again to -95 °C and trimethyl borate (9.3 g, 90.0 mmol) was added. After stirring at -95 °C for 30 min, 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 h, 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.

[0282]

[0283] Scheme 20

[0284] Step 1 in the synthesis of the LCC of structure (M14)

[0285] Scheme 21 shows a general overview of the first step in the synthesis of the 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[triphenylphosphine]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 3 days. After adding bis[triphenylphosphine]palladium(II) chloride (1.5 g, 2.1 mmol), the reaction mixture was stirred at 80 °C for 8 h. 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-fluoro-2-fluoro-4-[3-fluoro-4-(4-propylphenyl)phenyl]benzene (41.3 g, 106.6 mmol) as a colorless solid in 92% yield.

[0286]

[0287] Scheme 21

[0288] Synthesis of the LCC (SML-405) of structure (M15)

[0289]

[0290] The LLC of structure (M15) (4-[(trans,trans)-4'-propyl[1,1'-bicyclohexyl]-4-yl]-benzylamine) was prepared according to the procedure of Kanie, Kiyoshi et al., Chemistry Letters 1995, 24, 683.

[0291] Synthesis of LCC (SML-406) of structure (M16)

[0292]

[0293] The LLC 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 8741176 B2.

[0294] Synthesis of LCC (SML-407) of structure (M17)

[0295] The LLC of structure (M17) (2'-fluoro-4”-pentyl-[1,1':4',1”-terphenyl]-4-amine) was synthesized according to the procedure for 2'-fluoro-4”-propyl-[1,1':4',1”-terphenyl]-4-amine described in Wang, Chun-Chih et al., US 8741176 B2.

[0296]

Claims

1. A patterned liquid crystal monolayer structure (100) on a patterned substrate (900), comprising: The patterned substrate (900), which comprises 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); Wherein the liquid crystal compound (300) consists of a columnar straight-chain organic liquid crystal core structure containing at least one 1,4-phenylene moiety (700), the 1,4-phenylene moiety being attached to a straight-chain alkyl group (600) containing at least two carbons at one end and to a polar anchoring group (800) at the other end, the polar anchoring group being selected from the group consisting of a phosphonate-containing moiety, a phosphonic acid-containing moiety, a thiol-containing moiety, an amino-containing moiety, a moiety containing at least one alkylene hydroxyl group, and a moiety containing an alkyl-polyol; Wherein in the self-assembled monolayer (200), the liquid crystal compounds (300) are arranged in the self-assembled monolayer (200) such that each liquid crystal compound is parallel to each other and points in the same direction in the self-assembled monolayer (200), perpendicular to the patterned substrate (900) and attached to the surface region (500) only through the polar anchoring group (800); and Wherein any one of the following, When the polar anchoring group (800) is an alkyl-polyol coordination moiety or a moiety containing at least one alkylene hydroxyl group, the surface region (500) to which the self-assembled monolayer (200) is attached is a surface region based on a non-metallic inorganic silicon compound, and the surface region (400) free of the liquid crystal compound (300) is a metal surface region, or When the polar anchoring group is selected from the group consisting of a phosphonate-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 metal surface region, and the surface region (400) free of the liquid crystal compound (300) is a surface region based on a non-metallic inorganic silicon compound.

2. The patterned single-layer structure on the substrate as described in claim 1, wherein, The straight-chain alkyl group (600) is a C-2 to C-5 alkyl group.

3. The patterned single-layer structure on the substrate according to claim 1 or 2, wherein, The columnar straight-chain organic liquid crystal core structure containing at least two 1,4-phenylene moieties (700) is selected from structures (I), (II), (IIa), (III), (IV), (V), (VI), (VII), and (VIII), where ** is the attachment point of the straight-chain alkyl group (600) and * is the attachment point of the polar anchoring group (800), and R1 and R2 are independently selected from H, C-1 to C-2 alkyl groups, and F, 4. The patterned single-layer structure on the substrate according to any one of claims 1 to 3, wherein, The polar anchoring group (800) is selected from structure (Ip), structure (Ipa), structure (IIp), and structure (IIpa), where L1 and L2 are independently selected from C-2 to C-4 straight-chain alkylene spacer groups, and *** is the attachment point of the polar anchoring group to the liquid crystal compound, 5. The patterned single-layer structure on the substrate according to any one of claims 1 to 3, wherein, The polar anchoring group (800) is selected from structure (IIIp), structure (IVp), structure (Vp), structure (VIp), structure (VIIp), structure (VIIIp) and structure (IXp), where L3, L4, L5, L6 and L7 are each independently selected from C-2 to C-4 straight-chain alkylene spacers, *** is the attachment point of the polar anchoring group (800) to the liquid crystal compound (300), R p1 is C-1 to C-4 alkoxy, and R p2 is C-1 to C-4 alkyl or C-1 to C-4 alkoxy, ***L3——SH(IIIp) ***O——L4——SH(IVp) ***NH2(VIIp) ***L6—NH2(VIIIp) ***O—L7—NH2(IXp).

6. The patterned single-layer structure on a substrate according to any one of claims 1 to 4, wherein, The liquid crystal compound (300) is a compound selected from compounds having structures (M1), (M2), (M3), (M4), (M5), and (M7), 7. The patterned single-layer structure on a substrate according to any one of claims 1 to 3 and 5, wherein, The liquid crystal compound (300) is a compound selected from compounds having structures (M8), (M9), (M10), (M11), (M12), (M13), and (M14), 8. The patterned single-layer structure on a substrate according to any one of claims 1 to 4 and 6, wherein, The surface region (500) covered with SAM is a surface region based on a non-metallic inorganic silicon compound selected from silicon oxide (SiO2), silicon with native oxide, silicon nitride (SiN), and silicon oxynitride (SiON), and the surface region (400), which is bare, is a metal selected from tungsten, gold, silver, copper, cobalt, ruthenium, zirconium, titanium, and hafnium.

9. The patterned single-layer structure on a substrate according to any one of claims 1 to 3, 5 and 7, wherein, The surface region (500) covered with SAM is a metal selected from tungsten, gold, silver, copper, cobalt, ruthenium, zirconium, titanium, and hafnium, and the surface region (400), which is bare, is a surface region based on a non-metallic inorganic silicon compound selected from silicon oxide (SiO2), silicon with native oxide, silicon nitride (SiN), and silicon oxynitride (SiON).

10. A composition comprising a liquid crystal compound (300) and an organic spin-casting solvent, wherein the liquid crystal compound consists of a columnar linear organic liquid crystal core structure comprising at least one 1,4-phenylene moiety (700), the 1,4-phenylene moiety being attached at one end to a linear alkyl group (600) having at least two carbons and at the other end to a polar anchoring group (800).

11. The composition according to claim 10, wherein, The linear alkyl group (600) is a C-2 to C-5 alkyl group.

12. The composition according to any one of claims 10 or 11, wherein, The columnar linear organic liquid crystal core structure comprising at least two 1,4-phenylene moieties (700) is selected from structures (I), (II), (IIa), (III), (IV), (V), (VI), (VII), and (VIII), where ** is the attachment point of the linear alkyl group (600) and * is the attachment point of the polar anchoring group (800), and R1 and R2 are independently selected from H, C-1 to C-2 alkyl groups, and F, 13. The composition according to any one of claims 10 to 12, wherein, The polar anchoring group (800) is selected from structures (Ip), (Ipa), (IIp), and (IIpa), where L1 and L2 are independently selected from C-2 to C-4 linear alkylene spacers, and *** is the attachment point of the polar anchoring group (800) to the liquid crystal compound (300), 14. The composition according to any one of claims 10 to 12, wherein The polar anchoring group (800) is selected from structure (IIIp), structure (IVp), structure (Vp), structure (VIp), structure (VIIp), structure (VIIIp), and structure (IXp), where L3, L4, L5, L6, and L7 are each independently selected from C-2 to C-4 straight-chain alkylene spacers, *** is the attachment point of the polar anchoring group (800) to the liquid crystal compound (300), and R p1 is C-1 to C-4 alkoxy, and R p2 is C-1 to C-4 alkyl or C-1 to C-4 alkoxy. ***NH2(VIIp) ***L6 NH2(VIIp) ***O-L7-NH2(IXp).

15. The composition according to any one of claims 10 to 12 and 13, wherein, The liquid crystal compound (300) is a compound selected from compounds having structures (M1), (M2), (M3), (M4), (M5), and (M7), 16. The composition according to any one of claims 10 to 12 and 14, wherein, The liquid crystal compound (300) is selected from compounds having structures (M8), (M9), (M10), (M11), (M12), (M13), and (M14), 17. The composition according to any one of claims 10 to 12, 13 and 15, wherein, The liquid crystal compound (300) is a compound having the structure (M4).

18. The composition according to any one of claims 10 to 12, 14 and 16, wherein, The liquid crystal compound (300) is a compound selected from compounds having the structures (M8), (M9), (M12), (M13), and (M14).

19. The composition according to any one of claims 10 to 12, 14 and 16, wherein, The liquid crystal compound (300) is a compound selected from compounds having the structures (M10) and (M11).

20. The composition according to any one of claims 10 to 12, 13, 15 and 17, wherein, The organic spin-coating solvent is a single organic solvent or a mixture of at least two organic solvents selected from the group consisting of: 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, or diethylene glycol dimethyl ether; glycol ether ester derivatives such as ethyl cellosolve acetate, methyl cellosolve acetate, or propylene glycol monomethyl ether acetate (PGMEA). Carboxylic acid esters of monobasic acids selected from ethyl acetate, n-butyl acetate, and amyl acetate. Carboxylic acid esters of dibasic acids selected from diethyl oxalate and diethyl malonate. Dicarboxylic acid esters of diols selected from ethylene glycol diacetate and propylene glycol diacetate. Hydroxycarboxylic acid esters selected from methyl lactate, ethyl lactate (EL), ethyl glycolate, and ethyl 3-hydroxypropionate. Ketone esters selected from methyl pyruvate and ethyl pyruvate. Alkoxycarboxylic 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, and diacetone alcohol methyl ether. Ketol derivatives selected from acetol and diacetone alcohol. Ketals or acetals selected from 1,3-dioxolane and diethoxypropane, and butyrolactone. Amides selected from dimethylacetamide and dimethylformamide, and Anisole.

21. The composition according to any one of claims 10 to 12, 13, 15, 17 and 20, wherein, The liquid crystal compound is present in a loading amount of about 0.5 wt.% to about 2.0 wt.%.

22. The composition according to 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. The composition according to 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 wt.% PGME and 30 wt.% PGMEA.

24. The composition according to any one of claims 10 to 12, 14, 16 and 18, wherein, The organic spin-coating solvent is a single organic solvent or a mixture of at least two organic solvents selected from the group consisting of: 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, or diethylene glycol dimethyl ether. Glycol ether ester derivatives such as ethyl cellosolve acetate, methyl cellosolve acetate, or propylene glycol monomethyl ether acetate (PGMEA). Carboxylic acid esters of monobasic acids selected from ethyl acetate, n-butyl acetate, and amyl acetate. Carboxylic acid esters of dibasic acids selected from diethyl oxalate and diethyl malonate. Dicarboxylic acid esters of diols selected from ethylene glycol diacetate and propylene glycol diacetate. Hydroxycarboxylic acid esters selected from methyl lactate, ethyl lactate (EL), ethyl glycolate, and ethyl 3-hydroxypropionate. Ketone esters selected from methyl pyruvate and ethyl pyruvate. Alkoxycarboxylic 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, 2-heptanone, and diacetone alcohol methyl ether, Ketol derivatives selected from acetol and diacetone alcohol, Ketals or acetals selected from 1,3-dioxolane and diethoxypropane, butyrolactone, Amides selected from dimethylacetamide and dimethylformamide, and Anisole.

25. The composition according to any one of claims 10 to 12, 14, 16, 18 and 24, wherein The liquid crystal compound is present in a loading amount of about 0.5 wt.% to about 2.0 wt.%.

26. The composition according to 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. The composition according to 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 wt.% PGME and 30 wt.% PGMEA.

28. A method for selectively forming a self-assembled monolayer (SAM) of liquid crystal (LC) on a non-metallic region in a hybrid substrate comprising both a metallic region and a non-metallic region, the method comprising the steps of: i) Spin-coating the composition according to any one of claims 10 to 12, 13, 15, 17, 20, 21, 22, and 23 on the hybrid substrate, wherein the polar anchoring group (800) is an alkyl-polyol coordination moiety or a moiety comprising at least one alkylene hydroxyl, and wherein the non-metallic region is selected from silica, silicon with native oxide, silicon nitride, and silicon oxynitride, and the metallic region is selected from tungsten, gold, silver, copper, cobalt, ruthenium, zirconium, titanium, and hafnium, ii) Baking for about 2 min to about 10 min at a temperature ranging from about 150 °C to about 180 °C under an inert gas, iii) Rinsing 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 region and the non-metallic region, vi) Rinsing the substrate with a dilute aqueous solution of an acid to selectively remove the self-assembled monolayer of liquid crystal on the metallic region, vii) Rinsing the substrate with water and air-drying to obtain a substrate in which only the non-metallic region has an SAM of LC.

29. A method for selective atomic layer deposition on a metallic region of a hybrid substrate comprising both a metallic region and a non-metallic region, the method comprising the steps of: ia) Preparing a hybrid substrate in which the non-metallic region has a self-assembled monolayer of liquid crystal according to claim 28, iia) Using atomic layer deposition technology to more selectively deposit a metal oxide on the metallic region that does not have a self-assembled monolayer of liquid crystal.

30. The method according to claim 29, wherein, The atomic layer deposition technology is a technology employing deposition of about 10 to about 50 deposition cycles, wherein each cycle employs the following treatments at a temperature of about 250 °C to about 350 °C: treatment with (MeCp)2Hf(OMe)Me vapor for about 1 to about 5 s; subsequent treatment with N2 for about 5 s to about 15 s; treatment with H2O for about 1 s to about 5 s; and treatment with N2 for about 5 s to about 15 s.

31. A method for selectively forming a self-assembled monolayer (SAM) of liquid crystal (LC) on a metal region in a hybrid substrate containing both metal regions and non-metal regions, the method comprising the steps of: ib) Spin-coating the composition according to claims 14, 16, 18, 19, 23, 24, 25 and 26 on the hybrid substrate, wherein the polar anchoring group (800) is selected from moieties containing phosphonates, moieties containing phosphonic acids, moieties containing thiols and moieties containing amines, and wherein the non-metal regions are selected from silicon dioxide, silicon with native oxide, silicon nitride and silicon oxynitride, and the metal regions are selected from tungsten, gold, silver, copper, cobalt, ruthenium, zirconium, titanium and hafnium, iib) Bake at a temperature in the range from about 150 °C to about 180 °C for about 2 min to about 10 min under an inert gas, iiib) Rinse with an organic spin-coating solvent, ivb) Air-dry the substrate, vb) Repeat steps ib) to ivb) twice, vib) Air-dry the substrate to obtain a self-assembled monolayer of liquid crystal only on the metal regions of the substrate.

32. A method for selective atomic layer deposition on a non-metal region of a hybrid substrate containing both metal regions and non-metal regions, the method comprising the steps of: ic) Prepare a hybrid substrate, wherein the metal region has a self-assembled monolayer of liquid crystal according to claim 31, iic) Use atomic layer deposition techniques to more selectively deposit a metal oxide on the non-metal regions that do not have a self-assembled monolayer of liquid crystal.

33. The method according to claim 32, wherein, The atomic layer technique is a technique of deposition using about 10 to about 50 deposition cycles, wherein each cycle uses the following treatments at a temperature in the range from about 250 °C to about 350 °C: treatment with (MeCp)2Hf(OMe)Me vapor for about 1 to about 5 s; subsequent treatment with N2 for about 5 s to about 15 s; treatment with H2O for about 1 s to about 5 s; and treatment with N2 for about 5 s to about 15 s.

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

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