Two-bit memory device and method of operating a two-bit memory device and electronic assembly

Abstract

A two-bit memory device (1) having a layer structure (10) is proposed. The layer structure (10) comprises, in this order, a bottom layer (A), a molecular layer (C) containing a chiral compound having at least one polar functional group, and a top layer (E). The top layer (E) is conductive and ferromagnetic. The chiral compound of the molecular layer (C) acts as a spin filter for electrons passing through the molecular layer (C). The chiral compound has a flexible conformation and a conformational flexible molecular dipole moment. The layer structure (10) has at least four different states of resistance to current flowing from the bottom layer (A) to the top layer (E), depending on the magnetization of the top layer (E) and the orientation of the conformational flexible dipole moment of the chiral compound of the molecular layer (C). A further aspect of the invention relates to a method of operating the two-bit memory device and an electronic assembly comprising at least one two-bit memory device.

Description

[0001] This invention relates to a two-bit memory device having a layered structure, wherein the layered structure comprises, in sequence, a bottom layer, a sublayer, and a top layer. A further aspect of the invention relates to a method of operating the two-bit memory device and an electronic assembly comprising at least one two-bit memory device.

[0002] In computer technology, storage media capable of quickly writing to and reading from the information stored within are needed. Solid-state memory, or semiconductor memory, enables particularly fast and reliable storage media because it requires absolutely no moving parts. Currently, Dynamic Random Access Memory (DRAM) is primarily used. DRAM allows for fast access to stored information, but this information must be updated periodically, meaning that the stored information is lost when power is cut off.

[0003] Existing technologies also disclose non-volatile semiconductor memories, such as flash memory or magnetoresistive random access memory (MRAM), in which information is retained even after power is cut off. One drawback of flash memory is that write access is relatively slow and flash memory cells cannot be erased indefinitely. The lifespan of flash memory is typically limited to a maximum of one million read / write cycles. MRAM can be used similarly to DRAM and has a long lifespan, but this type of memory has not yet established its position due to its difficult manufacturing process.

[0004] Another alternative is memory that operates on the basis of memristors. The term memristor is an abbreviation of the words "memory" and "resistor" and refers to a component that can reproducibly change its resistance between high and low resistance. Maintaining its respective state (high or low resistance) even without a supplied voltage means that non-volatile memory can be implemented using memristors.

[0005] David H. Waldeck's article "Chiral-Induced Spin Selectivity Effect," J. Phys. Chem. Lett. 2012, 3, 2178-2187, describes the recently established experimental and theoretical chiral-induced spin selectivity (CISS) effect. Experiments have shown that ordered films of chiral organic molecules on surfaces can act as spin filters at room temperature. Furthermore, a storage device is proposed comprising a ferromagnetic nanoobject disposed between two electrodes and connected to the electrodes via chiral molecules having all the same chirality. When charge flows through the electrodes, chiral molecules, and nanoobject, a preferred spin is transferred and can be used to induce magnetization of the nanoobject. Since the preferred orientation of the spin depends on the direction of charge flow, the magnetization direction depends on the direction of current. After the nanoobject is magnetized, a small current flowing in the same direction will have high resistance, while a small current flowing in the opposite direction will have low resistance because its spin corresponds to a minority of spins in the nanoobject.

[0006] EP 2 492 984 A2 discloses a spin filter device comprising a substrate and at least one monolayer containing chiral molecules. The chiral molecules act as spin filters, allowing electrons exhibiting predetermined spins to pass through. In one embodiment, the device has a first substrate, a monolayer of asymmetric molecules, and a second substrate. The first substrate may be made of metal or semiconductor and serves as the source material. The second substrate serves as the target material. Electrons enter the monolayer from the first substrate. Most of the electrons that have passed through the monolayer have the same spin. These spin-filtered electrons are injected into the second substrate.

[0007] US 2015 / 049542 A1 discloses a spin-selective device. The device comprises a first layer containing a ferromagnetic material and a second layer coupled to the first layer. The second layer includes at least one molecule having a specified chirality, such that when a current flows between the first and second layers, one or more regions of the ferromagnetic material are magnetically polarized in a specific direction. Furthermore, storage and / or logic devices incorporating such a spin-selective device are disclosed. The second layer acts as a spin injector and provides a spin-polarized current. To inject a polarized current having a first spin polarization, a chiral molecule having a first chirality is provided; to inject a polarized current having a second spin polarization, a chiral molecule having a second chirality is provided. The chirality of these molecules is fixed and does not change during operation of the spin-selective device.

[0008] DE 10 2017 005 884 A1 discloses an electronic switching element comprising, in sequence, a first electrode, a molecular layer bonded to a substrate, and a second electrode. The molecular layer is essentially composed of compounds in which mesocrystalline groups are bonded to the substrate via spacer groups through anchoring groups. The resistance of the molecular layer can be switched between a high-resistance state and a low-resistance state by applying a potential exceeding the switching voltage.

[0009] To reduce the area required for flash memory cells, multilevel cell (MLC) technology is used, where a single cell stores more than one bit. However, this multilevel cell approach cannot be applied to fast-switching non-volatile magnetic memory technologies such as MRAM, spin torque transfer magnetoresistive random access memory (STT MRAM), or spin-orbit torque transfer magnetoresistive random access memory (SOT MRAM).

[0010] There is a need for compact and energy-efficient storage devices that provide non-volatile and fast-switching memory.

[0011] A two-bit memory device with a layered structure is proposed. The layered structure comprises, in this order, a bottom layer (A), a molecular layer (C) containing a chiral compound having at least one polar functional group, and a top layer (E).

[0012] The top layer (E) is conductive and ferromagnetic. The chiral compound in the molecular layer (C) acts as a spin filter for electrons passing through the molecular layer (C). This chiral compound has a flexible conformation and a conformationally flexible molecular dipole moment.

[0013] The layer structure has at least four different states of resistance to current flowing from the bottom layer (A) to the top layer (E), depending on the magnetization of the top layer (E) and the orientation of the flexible dipole moment of the chiral compound in the molecular layer (C).

[0014] The four different states of the resistor in this layered structure can be used to encode 2 bits of information, where each bit can be either "0" or "1". For example, the two states of the molecular layer (C) can encode the state of the first bit, and the two states of the top layer (E) can encode the state of the second bit.

[0015] The proposed two-bit storage device has a non-volatile state, meaning that no refresh cycle or supply voltage is required to maintain the state and thus retain the encoded information.

[0016] The resistance of the molecular layer (C) depends on the orientation of the at least one polar functional group of the chiral compound. The at least two resistance states of the molecular layer (C) can be addressed by conformational dipole rearrangement of the at least one polar functional group of the chiral compound. This can be achieved by applying an electric field. This is called dielectric switching. Switching occurs when the applied voltage is equal to or exceeds the switching voltage.

[0017] Similarly, the two resistance states of the top layer (E) can be addressed by changing the magnetization of the top layer (E), for example by means of an external magnetic field or preferably by means of a spin-torque effect. This is called magnetic switching. Depending on the magnetization of the top layer (E), the spin-polarized current flowing into the top layer (E) from the molecular layer (C) exhibits either low or high resistance.

[0018] The molecular layer (C) of the present invention preferably comprises chiral and enantiomerically pure, or at least enriched, chiral compounds. Chiral molecules cannot overlap on their mirror images. The molecular layer preferably comprises organic chiral compounds having conformationally flexible dipole moments that can switch along the z-axis, i.e., in a plane perpendicular to the layer structure.

[0019] Chiral compounds may contain conformationally flexible spacer groups, which allow the at least one polar group to change its orientation when an electric field is applied. The resistance of the molecular layer (C) depends on the orientation of the polar group and can therefore be switched by means of an electric field.

[0020] The chiral molecules of the molecular layer (C) act as electron spin filters. When an electric current flows through the molecular layer (C) perpendicular to the plane of this layer, the electron spins are polarized due to the chiral-induced spin selectivity (CISS) effect, so that most electrons have the same spin. Typically, the electron spin of the current is unpolarized, meaning that, apart from statistical fluctuations, the number of electrons in the "spin-up" state is equal to the number of electrons in the "spin-down" state. The degree of spin polarization of the current is defined as the quotient of the difference between the current I+ with "spin-up" and the current I- with "spin-down" and the sum of the currents I+ and I-.

[0021] Preferably, the current passing through the molecular layer (C) has a spin polarization of at least 5%, more preferably at least 10%, and most preferably at least 25%.

[0022] The preferred thickness of the molecular layer (C) is 10 nm or less, preferably 5 nm or less, and more preferably 2 nm or less.

[0023] Preferably, the molecular layer (C) consists only of chiral components.

[0024] Preferably, the molecular layer (C) is an enantiomerically pure layer, but the molecular layer (C) may also consist of a mixture of achiral compounds, racemic compounds and chiral compounds, provided that at least 0.1% of the composition is enantiomerically pure and thus forms an enantiomeric excess.

[0025] The molecular layer (C) used according to the present invention is preferably a molecular monolayer. More preferably, the molecular layer (C) is a self-assembled monolayer (SAM). The production of self-assembled monolayers is known to those skilled in the art; a review is given, for example, in Abraham Ulman, “Formation and Structure of Self-Assembled Monolayers”, Chem. Rev. 1996, 96, 1533-1554.

[0026] Preferably, the molecular layer (C) is bonded to the substrate.

[0027] Preferably, the chiral compound of the molecular layer (C) is bonded to the bottom layer (A) so that the bottom layer (A) acts as a substrate.

[0028] Alternatively, preferably, an anchoring layer (B) for bonding the chiral compound of the molecular layer (C) is disposed between the bottom layer (A) and the molecular layer (C), and the chiral compound of the molecular layer (C) is bonded to the anchoring layer (B). In this case, the anchoring layer (B) acts as a substrate.

[0029] The anchoring layer (B) is preferably a thin layer of conductive material. Alternatively, the anchoring layer (B) may be selected from a thin layer of electrically insulating or semiconductor material. In the latter case, the material and thickness of the anchoring layer (B) are selected so that current can tunnel from the bottom layer (A) through the anchoring layer (B) into the molecular layer (C).

[0030] Preferably, the chiral compound is bonded to the substrate via chemisorption, particularly via addition or condensation reactions.

[0031] Alternatively, chiral compounds can bind to the substrate through physical adsorption.

[0032] Chiral compounds may contain anchoring groups to bind to the substrate.

[0033] The substrate coverage is preferably 90% or more to 100%, particularly preferably 95% or more to 100%, and especially preferably 98% or more to 100%.

[0034] Optionally, an intermediate layer (D) is disposed between the molecular layer (C) and the top layer (E). The intermediate layer (D) can be used to provide a protective layer for the molecular layer (C). For example, a thin intermediate layer can protect the molecular layer (C), particularly chiral compounds, when the top layer (E) is fabricated by a deposition method, such as physical or chemical vapor deposition.

[0035] Additionally or alternatively, the intermediate layer (D) can be used to modulate the electrical properties of the layer structure. For example, an extremely thin layer, typically about 2 nm thick, can be provided to reduce leakage current or prevent short circuits, while still allowing electrons to tunnel through the intermediate layer (D). This can improve the reliability of two-bit memory devices.

[0036] Furthermore, the intermediate layer (D) can act as an intermediate layer to enhance adhesion and improve the reliability of binary memory devices, especially relative to thermal stress during the manufacturing process.

[0037] Preferably, the materials of the anchoring layer (B) and / or the intermediate layer (D) are selected from Al2O3, ZrO2, HfO2, TiO2, SiO2, ITO, AZO, IGZO, ZnO, MgO and combinations thereof.

[0038] The materials for the anchoring layer (B) and the intermediate layer (D) can be selected independently of each other.

[0039] Especially when selecting electrical insulating materials for the anchoring layer (B) and / or intermediate layer (D), thin layers are preferred. Preferably, a thickness in the range of 0.1 nm to 10 nm is chosen. Such thin layers allow electrons to tunnel through the anchoring layer (B) and / or intermediate layer (D) to allow tunneling current to flow.

[0040] The bottom layer (A) of the layer structure provides the electrical contacts of the layer structure and can also serve as the substrate of the molecular layer (C) without the use of the anchoring layer (B).

[0041] Preferably, the material of the bottom layer (A) is selected from doped Si, Al, W, Mo, Ru, Ag, Au, TiN, TaN and combinations thereof.

[0042] The top layer (E) of this layered structure is conductive and ferromagnetic. Preferably, the top layer (E) is a soft magnetic layer. Compared to hard magnetic layers, soft magnetic layers are easier to magnetize and have low coercivity.

[0043] Preferably, the material of the top layer (E) is selected from Ni, Co, Fe, NiFe, CoFeB, CoFe, GdFe, TbFeCo, GdFeCo and combinations thereof.

[0044] Preferably, the quotient of the difference between the resistances of the two states of the molecular layer (C) and the difference between the resistances of the two states of the top layer (E) is in the range of 10 to 10,000.

[0045] Preferably, the quotient between the difference between the high-resistivity state and the low-resistivity state of the molecular layer (C) is in the range of 20 to 1000, and more preferably in the range of 100 to 500.

[0046] Preferably, the quotient between the difference between the high-resistance state and the low-resistance state of the top layer (E) is in the range of 2 to 10, and more preferably in the range of 5 to 10.

[0047] In a first embodiment of the two-bit memory device, a bottom layer (A) is configured as a bottom electrode or connected to a bottom electrode, and a top layer is connected to a top electrode. To switch the molecular layer (C) to a first resistive state or a second resistive state, a first switching voltage or a second switching voltage is applied between the bottom layer (A) and the top layer (E), respectively. To switch the top layer (E) to the first resistive state or the second resistive state, a third switching voltage or a fourth switching voltage is applied between the bottom layer (A) and the top layer (E), respectively. The absolute values ​​of the third and fourth switching voltages are at least twice the absolute values ​​of the first and second switching voltages. The magnetic switching of the top layer (E) depends particularly on the spin polarization of the current supplied by the molecular layer (C) and the magnetic properties of the top layer (E), especially the coercivity. Accordingly, the third and fourth switching voltages can be tuned by selecting the materials of the molecular layer (C) and the top layer (E).

[0048] The third and fourth switching voltages must be different from the first and second switching voltages to independently address magnetic switching and dielectric switching.

[0049] Preferably, the bottom electrode includes exactly one electrical contact for applying a switching voltage and applying a read current.

[0050] The dielectric switching of the molecular layer (C) depends in particular on the chiral compound used and the electric field generated by the applied voltage. Accordingly, the required first and second switching voltages depend in particular on the thickness of the molecular layer (C) and the chiral compound. These parameters are adjusted so that the first and second switching voltages are below the dielectric breakdown voltage of the molecular layer (C).

[0051] In this first embodiment, the magnetic switching of the top layer (E) is achieved using a spin-polarized current via spin torque transfer. A chiral compound of the molecular layer (C) is used to spin-polarize the current via the CISS effect. The magnetic switching of the top layer (E) depends particularly on the magnetic properties of the material used, the current flowing when a third or fourth switching voltage is applied, and the degree of spin polarization of the current. Accordingly, the third and fourth switching voltages depend on the material of the top layer (E), the chiral compound, and the overall resistance of the layer structure.

[0052] In the second embodiment, the bottom layer (A) is configured as a bottom electrode or in contact with the bottom electrode (14), and the bottom electrode is in contact with the first electrical contact and additionally in contact with the second electrical contact and forms an electrical conductor arranged parallel to the top layer (E), and the first and second electrical contacts are arranged such that when a third switching voltage or a fourth switching voltage is applied between the first and second electrical contacts respectively, current flows through the electrical conductor.

[0053] In this second embodiment, dielectric switching is performed in the same manner as in the first embodiment. However, magnetic switching of the top layer (E) is performed using an external magnetic field generated by the current flowing through an electrical conductor arranged parallel to the top layer (E). The magnetic switching, and therefore the third and fourth switching voltages, depend in particular on the magnetic properties of the material of the top layer (E), the distance between the top layer (E) and the electrical conductor, and the resistance of the electrical conductor.

[0054] The material of the top electrode and / or bottom electrode is conductive and preferably selected from metallic conductors or semiconductors.

[0055] The top and / or bottom electrodes can also be configured as a combination of materials (layer stack). The material can be selected from those suitable as the bottom layer (A). Further suitable examples include Hg, In, Ga, InGa, Ag, Au, Cr, Pt, PdAu, Pb, Al, Mg, TiN, TaN, W, Mo, Ru, CO, Ti, CNT, graphene, and conductive polymers (such as PEDOT:PSS).

[0056] The proposed two-bit memory device can be arranged on an outer substrate material, which can be, for example, a wafer.

[0057] The material of the outer substrate can be selected from elemental semiconductors such as silicon (Si), germanium (Ge), diamond, carbon in the form of graphite or graphene, compound semiconductors, especially II-VI compound semiconductors such as cadmium selenide (CdSe) and zinc sulfide (ZnS), metals such as gold, silver, copper, aluminum, and magnesium, or conductive oxide materials such as indium tin oxide (ITO), indium gallium oxide (IGO), indium gallium zinc oxide (IGZO), aluminum-doped zinc oxide (AZO), or fluorine-doped tin oxide (FTO). Crystalline silicon is preferred as the substrate, with silicon wafers having a (100) surface being particularly preferred. Silicon wafers with a (100) surface orientation are used as conventional substrates in microelectronics and can be obtained with high quality and a low surface defect ratio.

[0058] Suitable compound semiconductors include

[0059] III-V group semiconductors, such as GaAs, GaP, InP, InSb, InAs, GaSb, GaN, AlN, InN, Al x Ga (1-x) As and In x Ga (1-x) Ni,

[0060] II-VI group semiconductors, such as ZnO, ZnS, ZnSe, ZnTe, CdS, CdSe, CdTe, and Hg. (1-x) Cd (x) Te, BeSe, BeTe xand HgS;

[0061] III-VI semiconductors, such as GaS, GaSe, GaTe, InS, and InSe. x and InTe,

[0062] Group I-III-VI semiconductors, such as CuInSe2, CuInGaSe2, CuInS2, and CuInGaS2.

[0063] IV-IV group semiconductors, such as SiC and SiGe, and

[0064] IV-VI group semiconductors, such as SeTe.

[0065] The proposed two-bit memory device can be manufactured, for example, using photolithography, a method commonly known in the microelectronics industry.

[0066] Chiral compounds of the molecular layer (C) are preferably selected from compounds of the following formula.

[0067] R 1 -(A 1 -Z 1 ) r -B 1 -(Z 2 -A 2 ) s -Sp A -G (IA)

[0068] D 1 -Z D -(A 1 -Z 1 ) r -B 1 -(Z 2 -A 2 ) s -Sp-G (IB)

[0069] R 1C -(A 1 -Z 1 ) r -B 1 -Z L -A 2C -(Z 3 -A 3 ) s -G (IC)

[0070] in

[0071] R 1This refers to straight-chain or branched racemic or branched non-racemic alkyl or alkoxy groups, each having a maximum of 20 carbon atoms, wherein one or more CH2 groups among these groups can be independently converted by -C≡C-, -CH=CH-, ... -O-, -S-, -CF2O-, -OCF2-, -CO-O-, -O-CO-, -SiR 0 R 00 -、-NH-、-NR 0 - or -SO2- is substituted in such a way that the O atoms are not directly connected to each other, and one or more of the H atoms can be replaced by halogens, CN, SCN, or SF5.

[0072] R 1C This refers to straight-chain or branched racemic or branched non-racemic alkyl or alkoxy groups, each having 1 to 20 carbon atoms. One or more CH2 groups among these groups can be independently converted to -C≡C-, -CH=CH-, or ... -O-, -S-, -CF2O-, -OCF2-, -CO-O-, -O-CO-, -SiR 0 R 00 -、-NH-、-NR 0 - or -SO2- is replaced by O atoms that are not directly connected to each other, and one or more H atoms can be replaced by halogens, CN, SCN, or SF5, and alternatively refers to the D group. 1 -Z D ,

[0073] Z D With Z 1 Z 2 and Z 3 One meaning may refer to a spacer group.

[0074] Z 1 Z 2 Z 3 Each occurrence may represent a single bond, -CF2O-, -OCF2-, -CF2S-, -SCF2-, -CH2O-, -OCH2-, -C(O)O-, -OC(O)-, -C(O)S-, -SC(O)-, or -(CH2). n1 -、-(CF2) n2 -, -CF2-CH2-, -CH2-CF2-, -CH=CH-, -CF=CF-, -CF=CH-, -CH=CF-, -(CH2) n3 O-, -O(CH2) n4-, -C≡C-, -O-, -S-, -CH=N-, -N=CH-, -N=N-, -N=N(O)-, -N(O)=N- or -N=CC=N-,

[0075] n1, n2, n3, and n4 are the same or different from 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10.

[0076] Z L This refers to -O-, -S-, -CH2-, -C(O)-, -CF2-, -CHF-, and -C(R). x -2-, -S(O)-, -SO2-, wherein the group -CHF- or the asymmetrically substituted group -C(R)- is present. x )2- can be racemic or non-racemic.

[0077] R 0 R 00 The same or different terms refer to alkyl or alkoxy groups having 1 to 15 carbon atoms, wherein, in addition, one or more hydrogen atoms may be replaced by halogens.

[0078] R x Each time it appears, it may represent H or a straight-chain or branched alkyl group having 1 to 6 carbon atoms, either the same or different.

[0079] D 1 This refers to a diamondoid group, preferably derived from lower diamondoids, and most preferably selected from diamondalkyl, dialantyl, and triamantyl, wherein one or more H atoms may be replaced by F, or optionally fluorinated alkyl, alkenyl, or alkoxy groups having up to 12 C atoms in each case, particularly...

[0080]

[0081] A 1 A 2 A 3 Each occurrence may be identical or different, representing an aromatic, heteroaromatic, alicyclic, or heteroaliphatic ring having 4 to 25 ring atoms. It may also contain fused rings and may be mono- or poly-substituted by Y.

[0082] A 2C It refers to an aromatic or heteroaromatic ring with 5 to 25 ring atoms, which may also contain fused rings and can be Y-shaped. C Single or multiple substitutions,

[0083] Y, in each occurrence, may refer to F, Cl, CN, SCN, SF5, or a straight-chain or branched alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy, or alkoxycarbonyloxy group having 1 to 12 carbon atoms, preferably F or Cl, optionally fluorinated in each case.

[0084] Y C The terms F, Cl, CN, SCN, SF5, or linear or branched, optionally fluorinated in each case, are represented by alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy, or alkoxycarbonyloxy, having 1 to 12 carbon atoms, or cycloalkyl or alkylcycloalkyl, each having 3 to 12 carbon atoms, preferably methyl, ethyl, isopropyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, trifluoromethyl, methoxy, or trifluoromethoxy.

[0085] B 1 It means

[0086]

[0087] Where R 0 and R 00 The same or different refer to alkyl groups having 1 to 6 carbon atoms.

[0088]

[0089]

[0090] These groups can be oriented in two directions.

[0091] L 1 To L 3 The elements are independently represented as F, Cl, Br, I, CN, SF5, CF3, or OCF3, preferably CF3, Cl, or F, where L 3 H can also be used as an alternative representation.

[0092] Sp A This refers to spacer groups or single bonds.

[0093] Sp refers to a chiral spacer group.

[0094] G refers to -OH, -CH(CH2OH)2, -C(CH2OH)3, -SH, -SO2OH, -OP(O)(OH)2, -PO(OH)2, -C(OH)(PO(OH)2)2, -COOH, -Si(OR x -3 or -SiCl3, -SO2OR V -OP(O)(OR) V 2. -PO(OR)V )2、-C(OH)(PO(OR V )2)2、-COOR V -Si(OR) V )3, preferably -PO(OH)2 or -C(OH)(PO(OH)2)2, very preferably -PO(OH)2

[0095] R V This refers to secondary or tertiary alkyl groups having 1 to 20 carbon atoms, preferably secondary or tertiary alkyl groups having 3 to 10 carbon atoms.

[0096] r and s are either 0, 1, or 2 each time they appear.

[0097] Where R in equation IA 1 and Sp A At least one of them is a chiral group, optionally, Z of formula IB D It is a chiral spacer group, and R in formula IC 1C and Z L At least one of them is chiral, and B is chiral. 1 It is polar.

[0098] G can act as an anchoring group for binding the compound to the substrate.

[0099] The term "diamondoids" refers to substituted and unsubstituted cage-like compounds of the adamantane series, including adamantane, disadamantane, triadamantane, tetraadamantane, pentaadamantane, hexaadamantane, heptaadamantane, octaadamantane, etc., encompassing all their isomers and stereoisomers. These compounds possess an "adamantane" topology, meaning their carbon atom arrangement can overlap on a segment of a face-centered cubic diamond lattice. Substituted adamantanes from the first of the series with one to four independently selected alkyl or alkoxy substituents are preferred.

[0100] Adamantanes include “lower adamantanes” and “higher adamantanes” (these terms are defined herein), as well as mixtures of any combination of lower and higher adamantanes. The term “lower adamantanes” refers to adamantane, disadamantane, and triadamantane, and any and / or all unsubstituted and substituted derivatives of adamantane, disadamantane, and triadamantane. These lower adamantane components do not exhibit any isomerism or chirality and are readily synthesized, which distinguishes them from “higher adamantanes.” The term “higher adamantanes” refers to any and / or all substituted and unsubstituted tetraadamantane components; any and / or all substituted and unsubstituted pentaadamantane components; any and / or all substituted and unsubstituted hexaadamantane components; any and / or all substituted and unsubstituted heptaadamantane components; any and / or all substituted and unsubstituted octaadamantane components; and mixtures of the above substances and isomers and stereoisomers of tetraadamantane, pentaadamantane, hexadamantane, heptaadamantane, and octaadamantane. Fort, Jr. et al. reviewed adamantane chemistry in "Adamantane: Consequences of the Diamondoid Structure," Chem. Rev. vol. 64, pp. 277–300 (1964). Adamantane is the smallest member of the adamantane class and can be considered a single cage-like crystalline subunit. Disadamantane contains two subunits, tripadamantane three, tetraadamantane four, and so on. Adamantane, dipadamantane, and tripadamantane have only one isomer, while tetraadamantane has four different isomers (two of which represent enantiomer pairs), i.e., four different ways of arranging the four adamantane subunits. The number of possible isomers increases non-linearly with each higher member of the adamantane class (pentadamantane, hexaadamantane, heptaadamantane, octaadamantane, etc.). Adamantane has been extensively studied and is commercially available. Research has been directed in many areas, such as the thermodynamic stability, functionalization, and properties of adamantane-containing materials. For example, Schreiber et al., New J. Chem., 2014, 38, 28-41, describe the synthesis of functionalized adamantanes and their use in forming large-area SAMs on silver and gold surfaces. In KTNarasimha et al., Nature Nanotechnology 11, March 2016, pp. 267-273, adamantane monolayers are described as effectively imparting enhanced field emission properties to metal surfaces due to the significant reduction in the work function of the metal.

[0101] The anchoring groups used in this paper are functional groups that adsorb or bind compounds to the substrate surface via physical adsorption, chemisorption, or chemical reaction. Such chemical reactions include in-situ conversion of the anchoring group precursor on the surface of the substrate or electrode.

[0102] In the sense of this invention, the spacer group is a flexible chain between the dipole portion and the anchoring group, which creates a separation between these substructures and, due to its flexibility, improves the mobility of the dipole portion after it is bonded to the substrate.

[0103] The spacer group can be branched or straight-chained. Chiral spacer groups are branched and optically active, i.e., non-racemic.

[0104] In this document, alkyl groups are straight or branched and have 1 to 15 carbon atoms, preferably straight and have 1, 2, 3, 4, 5, 6 or 7 carbon atoms unless otherwise specified, and are therefore preferably methyl, ethyl, propyl, butyl, pentyl, hexyl or heptyl.

[0105] In this document, alkoxy groups are straight-chain or branched and contain 1 to 15 carbon atoms. They are preferably straight-chain and have, unless otherwise specified, 1, 2, 3, 4, 5, 6 or 7 carbon atoms, and are therefore preferably methoxy, ethoxy, propoxy, butoxy, pentoxy, hexoxy or heptoxy.

[0106] In this document, the alkenyl group is preferably an alkenyl group having 2 to 15 carbon atoms, which is straight-chain or branched and contains at least one C-C double bond. It is preferably straight-chain and has 2 to 7 carbon atoms. Therefore, it is preferably vinyl, prop-1- or -2-enyl, but-1-, -2- or -3-enyl, pent-1-, -2-, -3- or -4-enyl, hex-1-, -2-, -3-, -4- or -5-enyl, hep-1-, -2-, -3-, -4-, -5- or -6-enyl. If the two carbon atoms of the C-C double bond are substituted, the alkenyl group can be in the form of E and / or Z isomers (trans / cis). Generally, the respective E isomers are preferred. Among the alkenyl groups, prop-2-enyl, but-2- or -3-enyl, and pent-3- or -4-enyl are particularly preferred.

[0107] In this document, ynyl means an ynyl group having 2 to 15 carbon atoms, which is straight-chain or branched and contains at least one C-C triple bond. 1- and 2-propynyl and 1-, 2- and 3-butynyl are preferred.

[0108] In formulas IA, IB, and IC, the preferred aryl groups are derived from, for example, parent structures such as benzene, naphthalene, tetrahydronaphthalene, 9,10-dihydrophenanthrene, fluorene, indene, and dihydroindene.

[0109] In formulas IA, IB, and IC, the preferred heteroaryl group is, for example, a five-membered ring, such as furan, thiophene, selenophene, oxazole, isoxazole, 1,2-thiazole, 1,3-thiazole, 1,2,3-oxadiazole, 1,2,4-oxadiazole, 1,2,5-oxadiazole, 1,3,4-oxadiazole, 1,2,3-thiadiazole, 1,2,4-thiadiazole, 1,2,5-thiadiazole, and 1,3,4-thiadiazole; or a six-membered ring, such as pyridine, pyridazine, pyrimidine, pyrazine, 1,3,5-triazine, 1,2,4-triazine, and 1,2,3-triazine. or fused rings, such as indole, isoindole, indazine, indazole, benzimidazole, benzotriazole, purine, naphzimidazole, benzoxazole, naphzimidazole, benzothiazole, benzofuran, isobenzofuran, dibenzofuran, thieno[2,3b]thiophene, thieno[3,2b]thiophene, dithieno[2,3b]thiophene, isobenzothiophene, dibenzothiophene, benzothiadiazo[2,3b]thiophene, 2H-chromene (2H-1-benzopyran), 4H-chromene (4H-1-benzopyran), and coumarin (2H-benzopyran-2-one), or combinations of these groups.

[0110] In formulas IA, IB, and IC, preferred alicyclic groups are cyclobutane, cyclopentane, cyclohexane, cyclohexene, cycloheptane, decahydronaphthalene, bicyclo[1.1.1]pentane, bicyclo[2.2.2]octane, spiro[3.3]heptane, and octahydro-4,7-methanoindane.

[0111] In formulas IA, IB, and IC, preferred heteroaliphatic groups are tetrahydrofuran, dioxolane, tetrahydrothiophene, pyran, dioxolane, dithiane, silinane, piperidine, and pyrrolidine.

[0112] A 1 and A 2 They are mutually independent and, in each occurrence, either identically or differently, particularly preferably selected from the following group:

[0113] a) 1,4-Phenylidene, wherein, in addition, one or two CH groups may be substituted with N, and wherein, in addition, one or more H atoms may be substituted with Y.

[0114] b) The group consisting of trans-1,4-cyclohexylene and 1,4-cyclohexenylene, wherein, in addition, one or more non-adjacent CH2 groups may be substituted with -O- and / or -S-, and wherein, in addition, one or more H atoms may be substituted with Y, and

[0115] c) The group consisting of 1,3-dioxolane-2,4-diyl, tetrahydrofuran-2,5-diyl, cyclobutane-1,3-diyl, 1,4-bicyclo[2.2.2]octadiyl, piperidine-1,5-diyl, and thiophene-2,5-diyl, wherein, in addition, one or more H atoms may be replaced by Y.

[0116] Where Y has the meaning indicated above under formula IA and preferably refers to F, Cl, CN or CF3.

[0117] In formula IA, Sp A Preferred refers to spacer groups.

[0118] The preferred spacer group Sp is selected from formula Sp'-X', such that the group G-Sp- of formula IA corresponds to formula G-Sp'-X'-, and the group D of formula IB... 1 -Sp- corresponds to equation D 1 -Sp'-X', and make Z in formula IC D In the case of spacer groups, group D of formula IC 1 -Z D - Corresponding to equation D 1 -Sp'-X'-,

[0119] in

[0120] Sp' refers to a straight-chain or branched alkylene group having 1 to 20, preferably 1 to 12, carbon atoms, optionally mono- or poly-substituted with F, Cl, Br, I, or CN, and wherein, in addition, one or more non-adjacent CH2 groups may be independently substituted with -O-, -S-, -NH-, or -NR. 0 -、-SiR 00 R 000 -, -CO-, -COO-, -OCO-, -OCO-O-, -S-CO-, -CO-S-, -NR 0 -CO-O-、-O-CO-NR 0 -、-NR 0 -CO-NR 0 -, -CH=CH- or -C≡C- are substituted in a way that O and / or S atoms are not directly connected to each other.

[0121] X' refers to -O-, -S-, -CO-, -COO-, -OCO-, -O-COO-, -CO-NR 00 -、-NR 00 -CO-、-NR 00 -CO-NR 00 -, -OCH2-, -CH2O-, -SCH2-, -CH2S-, -CF2O-, -OCF2-, -CF2S-, -SCF2-, -CF2CH2-, -CH2CF2-, -CF2CF2-, -CH=N-, -N=CH-, -N=N-, -CH=CR 00 -、-CY x =CY x‘-, -C≡C-, -CH=CH-COO-, -OCO-CH=CH- or single bonds

[0122] R 0 R 00

[0123] and R 000 Each of them independently represents H or an alkyl group having 1 to 12 carbon atoms, and

[0124] Y x and Y x‘ Each can be represented independently as H, F, Cl, or CN.

[0125] X' is preferably -O-, -S-, -CO-, -COO-, -OCO-, -O-COO-, -CO-NR 0 -、-NR 0 -CO-、-NR 0 -CO-NR 0 - or a single key.

[0126] The preferred achiral group Sp' is -(CH2). p1 -、-(CF2) p1 -、-(CH2CH2O) q1 -CH2CH2-、-(CF2CF2O) q1 -CF2CF2-, -CH2CH2-S-CH2CH2-, -CH2CH2-NH-CH2CH2- or -(SiR) 00 R 000 -O) p1- Where p1 is an integer from 1 to 12, q1 is an integer from 1 to 3, and R 00 and R 000 It has the meaning mentioned above.

[0127] The particularly preferred achiral group -X'-Sp'- is -(CH2). p1 -、-O-(CH2) p1 -、-(CF2) p1 -、-O(CF2) p1 -、-OCO-(CH2) p1 - and -OC(O)O-(CH2) p1 - where p1 has the meaning stated above.

[0128] Particularly preferred non-chiral groups Sp' are, for example, in each case, straight-chain ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, undecylene, dodecylene, octadecylene, perfluoroethylene, perfluoropropylene, perfluorobutylene, perfluoropentylene, perfluorohexylene, perfluoroheptylene, perfluorooctylene, perfluorononylene, perfluorodecylene, perfluoroundecylene, perfluorododecylene, perfluorooctadecylene, ethoxyethylene, methyleneoxybutylene, ethylthioethylene, ethylene-N-methyliminoethylene, 1-methylalkylene, vinylene, propenylene, and butenylene.

[0129] The particularly preferred group X' is -O- or a single bond.

[0130] The preferred sub-formulas of formula IA are shown below: IAa to IAf

[0131] R 1 -B 1 -Sp A -G IAa

[0132] R 1 -(A 1 -Z 1 )-B 1 -Sp A -G IAb

[0133] R 1 -(A 1 -Z 1 )2-B 1 -Sp A -G IAc

[0134] R 1 -B 1 -(Z 2 -A 2 )-Sp A -G IAd

[0135] R 1 -B 1 -(Z 2 -A 2 )2-Sp A -G IAe

[0136] R 1 -(A 1 -Z 1 )-B 1 -(Z 2 -A 2 -)-Sp A -G IAf

[0137] Where R1 A 1 A 2 B 1 Z 1 Z 2 Sp A And G has the meaning indicated above and preferably

[0138] A 1 and A 2 It means

[0139]

[0140] B 1 It means

[0141]

[0142]

[0143] These groups can be oriented in two directions.

[0144] R 1 It refers to alkyl groups having 1-15 carbon atoms, preferably 1-7 carbon atoms, especially CH3, C2H5, n-C3H7, n-C4H9, and n-C5H. 11 n-C6H 13 or n-C7H 15 Or, as defined below, the chiral group R*.

[0145] L 1 and L 2 Each can be independently represented as CF3, Cl, or F, where the group L 1 and L 2 At least one refers to F,

[0146] L 3 It refers to F.

[0147] Y 1 and Y 2 They can be represented independently of H, Cl, or F.

[0148] Z 1 Z 2 These can be used independently to represent single bonds, -CF2O-, -OCF2-, -CH2O-, OCH2-, or -CH2CH2-.

[0149] Sp A It refers to a straight-chain 1,ω-alkylene group or a chiral spacer group Sp* as defined below, having 1 to 12 carbon atoms.

[0150] G refers to -OH, -SH, -SO2OH, -OP(O)(OH)2, -PO(OH)2, -COH(PO(OH)2)2, -COOH, -Si(OR)3, or -SiCl3.

[0151] Where R 1 and Sp A At least one of them is chiral.

[0152] The most preferred sub-formulas of formula IA are sub-formulas IAa, IAb, and IAd.

[0153] The following shows examples of preferred compounds of formulas IAa to IAF:

[0154]

[0155]

[0156]

[0157]

[0158]

[0159] Where R 1 Sp A G has the meaning given above.

[0160] The preferred sub-formulas of formula IB are sub-formulas IBa to IBf:

[0161] D 1 -Z D -B 1 -Sp-G IBa

[0162] D 1 -Z D -(A 1 -Z 1 )-B 1 -Sp-G IBb

[0163] D 1 -Z D -(A 1 -Z 1 )2-B 1 -Sp-G IBc

[0164] D 1 -Z D -B 1 -(Z 2 -A 2 )-Sp-G IBd

[0165] D1 -Z D -B 1 -(Z 2 -A 2 )2-Sp-G IBe

[0166] D 1 -Z D -(A 1 -Z 1 )-B 1 -(Z 2 -A 2 )-Sp-G IBf

[0167] Where D 1 A 1 A 2 B 1 Z D Z 1 Z 2 Sp and G have the meanings stated above.

[0168] In formula IB and its sub-formulas, it is highly preferred that...

[0169] A 1 and A 2 The same or different means

[0170]

[0171] B 1 It means

[0172]

[0173] D 1 This refers to adamantyl or didamantyl, especially adamantyl.

[0174] L 1 and L 2 Each can be independently represented as CF3, Cl, or F, where the group L 1 and L 2 At least one refers to F,

[0175] L 3 It refers to F.

[0176] Y 1 and Y 2 They can be represented independently of H, Cl, or F.

[0177] Z DThis refers to single bonds, -C≡C-, -C(O)O-, -OC(O)-, -OCH2-, -CH2O-, -CH2CH2-, -CH2CH2CH2-, or -CH2CH2CH2CH2-, preferably -CH2O-, -C≡C-, or single bonds.

[0178] Z 1 Z 2 The following can be represented independently: single bond, -C(O)O-, -OC(O)-, -CF2O-, -OCF2-, -CH2O-, -OCH2-, -CH2CH2-, with single bonds being particularly preferred.

[0179] Sp refers to the chiral spacer group Sp* as defined below.

[0180] G-OP(O)(OH)2, -PO(OH)2, -COH(PO(OH)2)2.

[0181] The most particularly preferred sub-formulas of formula IB are IBa, IBb, and IBd, especially the following compounds:

[0182]

[0183]

[0184]

[0185] Where D 1 Z D And G has the meaning given above and preferably

[0186] D 1 It refers to adamantyl alkyl group.

[0187] Z D This refers to -CH2O-, -C≡C-, or single bonds.

[0188] G refers to -P(O)(OH)2 or -COH(P(O)(OH)2)2.

[0189] In formula IC and its sub-formulas, it is highly preferred that...

[0190] A 1 and A 3 The same or different means

[0191]

[0192] A 2 -Z L It means

[0193]

[0194] B 1 It means

[0195]

[0196] R 1C It is the chiral group R* as defined below.

[0197] L 1 and L 2 Whether they are the same or different, they refer to F, CF3, or Cl.

[0198] Y 1 and Y 2 Whether the meaning of Y is the same or different from the meaning given above, it preferably refers to H, F or Cl.

[0199] Y 3 and Y 4 Whether similar or different, having the above description of Y 3 and Y 4 One of the given meanings, and preferably, refers to methyl, ethyl, isopropyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclopentenyl, cyclohexyl, cyclohexenyl, methoxy, trifluoromethyl, trifluoromethoxy, or trifluoromethylthio.

[0200] Z L It refers to -O-.

[0201] Z 1 Z 2 These can be used independently to represent single bonds, -C(O)O-, -OC(O)-, -CF2O-, -OCF2-, -CH2O-, OCH2-, or -CH2CH2-, especially single bonds.

[0202] G refers to -OP(O)(OH)2, -PO(OH)2, or -COH(PO(OH)2)2.

[0203] The most preferred sub-formulas of IC are sub-formulas IC-1 to IC-6:

[0204]

[0205]

[0206] in

[0207] R 1C It has one of the meanings given above.

[0208] L 1 and L 2 Whether the references are the same or different, they refer to F, CF3, or Cl.

[0209] Y 3 and Y4 "Methyl" or "methyl" has one of the meanings given above, and preferably refers to methyl.

[0210] G refers to -PO(OH)2 or -COH(PO(OH)2)2.

[0211] Preferably, the chiral compound has an enantiomeric excess (ee) of more than 50%, more preferably more than 80%, 90% or 95%, more preferably more than 97%, and particularly more than 98%.

[0212] Chirality is achieved by a branched chiral group Sp of the above formula IA or IB having one or more, preferably one or two, and very preferably one asymmetric substituted carbon atom (or: asymmetric carbon atom, C*). It is referred to above and below as Sp*.

[0213] In Sp*, the asymmetric carbon atom is preferably attached to two differently substituted carbon atoms, hydrogen atoms, and substituents selected from halogens (preferably F, Cl, or Br), having 1 to 5 carbon atoms in each case, and alkyl or alkoxy groups and CN.

[0214] The chiral organic group Sp* preferably has the formula

[0215]

[0216] in

[0217] X' has the meaning of the above definitions of formulas IA and IB and preferably refers to -CO-O-, -O-CO-, -O-CO-O-, -CO-, -O-, -S-, -CH=CH-, -CH=CH-COO- or a single bond, more preferably -CO-O-, -O-CO-, -O- or a single bond, and very preferably -O- or a single bond.

[0218] Q and Q', whether identical or different, refer to a single bond or optionally fluorinated alkylene group having 1 to 10 carbon atoms, wherein the CH2 group not connected to X may also be replaced by -O-, -CO-, -O-CO-, -CO-O- or –CH=CH-, preferably an alkylene group or a single bond having 1 to 5 carbon atoms, particularly preferably –(CH2). n5 -or a single key,

[0219] n5 is 1, 2, 3, 4, 5, or 6.

[0220] Y refers to an optionally fluorinated alkyl group having 1 to 15 carbon atoms—one or both non-adjacent CH2 groups may also be replaced by -O-, -CO-, -O-CO-, -CO-O- and / or -CH=CH-, and the additional CN or halogen, preferably an optionally fluorinated alkyl or alkoxy group having 1 to 7 carbon atoms, -CN or Cl, particularly preferably -CH3, -C2H5, -CF3 or Cl.

[0221] Z in its formula IB D In an embodiment of a chiral non-racemic spacer group, group D 1 -Sp* Preferred formula

[0222]

[0223] The groups that appear have the meanings given above.

[0224] The chiral group R of formula IA above, having one or more, preferably one or two, and most preferably one asymmetric substituted carbon atom (or: asymmetric carbon atom, C*), is used. 1 Or the chiral group R of the above formula IC 1C Hereinafter referred to as R* implementing chirality.

[0225] In R*, the asymmetric carbon atom is preferably attached to two differently substituted carbon atoms, hydrogen atoms, and substituents selected from halogens (preferably F, Cl, or Br), having 1 to 5 carbon atoms in each case, and alkyl or alkoxy groups and CN.

[0226] The chiral organic group preferably has the formula...

[0227]

[0228] in

[0229] X' has the meaning defined in Formula I above and preferably refers to -CO-O-, -O-CO-, -O-CO-O-, -CO-, -O-, -S-, -CH=CH-, -CH=CH-COO- or a single bond, more preferably -CO-O-, -O-CO-, -O- or a single bond, and very preferably -O- or a single bond.

[0230] Q refers to a single bond or optionally fluorinated alkylene group having 1 to 10 carbon atoms, wherein the CH2 group not connected to X may also be replaced by -O-, -CO-, -O-CO-, -CO-O- or –CH=CH-, preferably an alkylene group having 1 to 5 carbon atoms or a single bond, particularly preferably -CH2-, -CH2CH2- or a single bond.

[0231] Y refers to an optionally fluorinated alkyl group having 1 to 15 carbon atoms—one or both non-adjacent CH2 groups may also be replaced by -O-, -CO-, -O-CO-, -CO-O- and / or -CH=CH-, and the additional CN or halogen, preferably an optionally fluorinated alkyl or alkoxy group having 1 to 7 carbon atoms, -CN or Cl, particularly preferably -CH3, -C2H5, -CF3 or Cl.

[0232] R Ch It refers to an alkyl group having 1 to 15 carbon atoms, different from Y, wherein one or two non-adjacent CH2 groups may be replaced by -O-, -CO-, -O-CO-, -CO-O- and / or -CH=CH-, preferably a straight-chain alkyl group having 1 to 10, particularly 1 to 7 carbon atoms, wherein the CH2 group attached to the asymmetric carbon atom may be replaced by -O-, -O-CO- or -CO-O-.

[0233] R in its Chinese IC 1C This refers to group D as defined above. 1 -Z D In the embodiments, the group R* has the formula D 1 -Sp*, where Sp* refers to a chiral non-racemic spacer group.

[0234] As described with respect to formula IB, the group D in formula IC 1 -Sp* Preferred formula

[0235]

[0236] Dia, Q, Y, and X' have the meanings defined above, and

[0237] Q' has the same or different meaning as Q given above.

[0238] Synthesis Examples

[0239] Example 1. The synthesis of phosphonic acid PA1 is described in WO 2018 / 007337 A2.

[0240]

[0241] Example 2

[0242] Step 1: (2S)-3-[2,3-difluoro-4-(4-pentylcyclohexyl)phenoxy]-2-methyl-prop-1-ol

[0243]

[0244] 2,3-Difluoro-4-(4-pentylcyclohexyl)phenol (11.07 g, 39.21 mmol) was dissolved in butanone (144 mL), and (R)-3-bromo-2-methylprop-1-ol (9.00 g, 58.81 mmol) was added, followed by the addition of potassium carbonate (21.68 g, 156.8 mmol, 4.0 equivalence) in a single batch. The mixture was then heated under reflux overnight. The reaction was filtered, concentrated to dryness, and the crude product was recrystallized from acetonitrile to yield (2S)-3-[2,3-difluoro-4-(4-pentylcyclohexyl)phenoxy]-2-methyl-prop-1-ol in colorless crystalline form.

[0245] 1 ¹H NMR (400MHz, DMSO-d⁶) δppm 0.85(3H,t,J=7.0Hz),0.93(3H,d,J=7.0Hz),0.96–1.08(2H,m),1.12–1.34( 9H,m),1.43(2H,qd,J=12.5,2.2Hz),1.67–1.84(4H,m),1.92–2.02(1H,m),2. 61–2.72(1H,m),3.35–3.43(2H,m),3.86(1H,dd,J=9.4,6.4Hz),3.99(1H,dd ,J=9.4,5.9Hz),4.60(1H,t,J=5.3Hz),6.88–6.96(1H,m),6.96–7.04(1H,m).

[0246] Step 2: 1-[(2R)-3-bromo-2-methyl-propoxy]-2,3-difluoro-4-(4-pentylcyclohexyl)benzene

[0247]

[0248] (2S)-3-[2,3-difluoro-4-(4-pentylcyclohexyl)phenoxy]-2-methyl-prop-1-ol (8.16 g, 23.02 mmol) was dissolved in dichloromethane (82.0 mL), and triphenylphosphine (6.64 g, 25.32 mmol, 1.1 equivalence) was added under nitrogen. The solution was cooled with ice, and carbon tetrabromide (8.40 g, 25.32 mmol) was added fractionally over 10 minutes. The cooling was removed, and the solution was warmed to room temperature. After 4 hours, triphenylphosphine (0.60 g) and carbon tetrabromide (0.76 g) were added, and the solution was stirred overnight at room temperature. The reaction mixture was concentrated to dryness, heptane (175 mL) was added, and the mixture was stirred at 50 °C for 1 hour. The solid was filtered off and washed with heptane (2 x 125 mL). The filtrate was concentrated to dryness, and the suspension was filtered through silica to produce 1-[(2R)-3-bromo-2-methyl-propoxy]-2,3-difluoro-4-(4-pentylcyclohexyl)benzene in the form of a colorless oil.

[0249] 1 H NMR (400MHz, CDCl3) δppm 0.91(3H,t,J=7.0Hz),1.01-1.14(2H,m),1.16(3H,d,J=6.8Hz),1.19-1.3 8(9H,m),1.44(2H,qd,J=12.8,3.3Hz),1.80-1.92(4H,m),2.29-2.41(1H,m ),2.75(1H,tt,J=12.2,2.9Hz),3.57(1H,dd,J=10.0,5.3Hz),3.62(1H,dd ,J=10.0,5.2Hz),3.95-4.00(2H,m),6.65-6.75(1H,m),6.81-6.91(1H,m).

[0250] Step 3: 1-[(2R)-3-diethoxyphosphoryl-2-methylpropoxy]-2,3-difluoro-4-(4-pentylcyclohexyl)benzene

[0251]

[0252] Sodium hydride (60%, 1.39 g) was added fractionally to a solution of diethyl phosphite (4.79 g, 34.72 mmol) in tetrahydrofuran (THF) (69 mL) over nitrogen atmosphere for 10 minutes, and the mixture was stirred at room temperature for 45 minutes. A solution of 1-[(2R)-3-bromo-2-methyl-propoxy]-2,3-difluoro-4-(4-pentylcyclohexyl)benzene (6.90 g, 16.53 mmol) in THF (69 mL) was added to the mixture over 5 minutes. The mixture was then stirred under reflux overnight. The reaction mixture was added to 10% aq NH4Cl (180 mL) and stirred for 10 minutes. Methyl tert-butyl ether (300 mL) was added, and the layers were separated. Organic matter was dried with MgSO4 and concentrated to dryness to produce an oil, which was purified by elution on silica with ethyl acetate (0-10%) / dichloromethane to produce 1-[(2R)-3-diethoxyphosphoryl-2-methylpropoxy]-2,3-difluoro-4-(4-pentylcyclohexyl)benzene in the form of a pale yellow oil.

[0253] 1H NMR (400MHz, CDCl3) δppm 0.89(3H,t,J=7.0Hz),0.99-1.13(2H,m),1.15-1.51(19H,m),1.70(1H,ddd,J=18.4,15.4,7.8Hz),1.77-1.92(4H,m),2.10(1H,ddd,J=18.9 ,15.4,5.7Hz),2.32-2.49(1H,m),2.73(2H,tt,J=12.1,3.0Hz),3.86- 3.97(2H,m),4.01-4.20(4H,m),6.62-6.71(1H,m),6.78-6.88(1H,m).

[0254] 31 P NMR (162MHz, CDCl3) δppm 30.77 (s).

[0255] Step 4: [(2R)-3-[2,3-difluoro-4-(4-pentylcyclohexyl)phenoxy]-2-methyl-propyl]phosphonic acid

[0256]

[0257] Trimethylsilyl bromide (24.3 mL, 183 mmol) was added dropwise to a solution of 1-[(2R)-3-diethoxyphosphoryl-2-methylpropoxy]-2,3-difluoro-4-(4-pentylcyclohexyl)benzene (8.70 g, 18.3 mmol) in dichloromethane (131 mL) over 10 minutes, and the solution was stirred overnight at room temperature. The reaction mixture was concentrated to dryness to produce a yellow waxy solid. The solid was dissolved in dichloromethane (200 mL) and methanol (150 mL), and the dichloromethane was slowly removed under slight vacuum at 40 °C. The solution was cooled to room temperature and then chilled overnight in a freezer with stirring in an ice / water bath for 1 hour. The precipitate was filtered and dried to give an off-white solid. 2 M HCl (5 mL) was added to the filtrate, and the mixture was stirred in an ice / acetone bath for 15 minutes, followed by filtration of the precipitate to give a white solid. The two batches of material were combined and recrystallized from acetonitrile (16 vols) and THF (1 vol). The precipitate was filtered, washed with acetonitrile (2 x 15 mL), and dried to produce [(2R)-3-[2,3-difluoro-4-(4-pentylcyclohexyl)phenoxy]-2-methyl-propyl]phosphonic acid as a white solid.

[0258] 1H NMR (400MHz, CD3OD) d ppm 0.91(3H,t,J=7.0Hz),1.01-1.14(2H,m),1.21(3H,d,J=6.8Hz),1.22-1.40 (9H,m),1.42-1.56(2H,m),1.66(1H,ddd,J=18.2,15.3,8.0Hz),1.76-1.94 (4H,m),2.03(1H,ddd,J=18.9,15.3,5.4Hz),2.29-2.46(1H,m),2.73(1H,t t,J=12.2,3.1Hz),3.88-4.03(2H,m),6.78-6.88(1H,m),6.88-6.98(1H,m).

[0259] 19 F NMR (377MHz, CD3OD) δppm -162.51 (d, J = 19.1Hz), -146.22 (d, J = 19.1Hz).

[0260] 31 P NMR (162MHz, CD3OD) δppm 28.44.

[0261] Example 3

[0262] Step 1: 2,3-Difluoro-4-[(2S)-2-methyloctyloxy]benzaldehyde

[0263]

[0264] Potassium carbonate (20.42 g, 147.77 mmol, 4.00 equivalence) was added in a single step to a solution of 2,3-difluoro-4-hydroxybenzaldehyde (5.84 g, 36.94 mmol) and (S)-4-methylbenzenesulfonic acid 2-methyloctyl ester (12.68 g, 42.48 mmol) in dimethylformamide (59 mL) under nitrogen atmosphere. The mixture was heated to 80 °C and stirred overnight. The reaction mixture was cooled, poured onto water (250 mL), and stirred for 5 minutes. The mixture was extracted with heptane (2 x 250 mL), and the organic matter was combined and washed with water (2 x 250 mL), dried (MgSO4), and concentrated to dryness to give a yellow oil, which was purified by elution on silica with dichloromethane (0-20%) / heptane to produce 2,3-difluoro-4-[(2S)-2-methyloctyloxy]benzaldehyde in the form of a colorless oil.

[0265] Step 2: 2,3-Difluoro-4-[(2S)-2-methyloctyloxy]phenol

[0266]

[0267] 2,3-Difluoro-4-[(2S)-2-methyloctyloxy]benzaldehyde (9.70 g, 34.11 mmol), dichloromethane (97.0 mL), and mCPBA (70%, 10.51 g, 60.92 mmol) were stirred overnight at 25 °C. The reaction mixture was filtered, the filtrate was concentrated to dryness, and then redissolved in tetrahydrofuran (93 mL). A solution of LiOH·H₂O (4.06 g, 96.87 mmol) in water (97 mL) was added in one step to the THF solution, and the solution was stirred at 25 °C for 1 hour. HCl (0.2 M, 500 mL) was added fractionally and stirred for 1 hour. The mixture was extracted with MTB ether (2 x 250 mL), the combined organic matter was washed with brine (2 x 250 mL), dried (MgSO₄), and concentrated to dryness to give a beige solid. Add heptane (100 mL), stir for 15 minutes, then filter off the solid and wash with heptane (3 x 15 mL). Concentrate the filtrate to dryness to give a brown oil (9.3 g). This is purified by elution on silica with dichloromethane / heptane (0-35%) to give 2,3-difluoro-4-[(2S)-2-methyloctyloxy]phenol in the form of a pale yellow oil, which crystallizes upon standing.

[0268] 1 H NMR(400MHz,DMSO-d6)δppm 0.81-0.91(3H,m),0.94(3H,d,J=6.7Hz),1.08-1.38(9H,m),1.38-1.51(1H,m),1.75-1.91(1H,m),3.73(1H,dd,J =9.4,6.7Hz),3.81(1H,dd,J=9.4,5.8Hz),6.66(1H,td,J=9.2,2.2Hz),6.78(1H,td,J=9.2,2.2Hz),9.77(1H,s).

[0269] Step 3: 1-(11-diethoxyphosphorylundecyloxy)-2,3-difluoro-4-[(2S)-2-methyloctyloxy]benzene

[0270]

[0271] Diethyl 11-bromoundecyl)phosphonate (6.75 g, 19.99 mmol) was added to 2,3-difluoro-4-[(2S)-2-methyloctyloxy]phenol (4.95 g, 181.18 mmol) in methyl ethyl ketone (65 mL), followed by a one-time addition of potassium carbonate (10.05 g, 72.71 mmol). The mixture was heated under reflux overnight, filtered, and concentrated to dryness to produce a brown oil, which was purified by elution on silica with ethyl acetate (0-20%) / dichloromethane to yield 1-(11-diethoxyphosphorylundecyloxy)-2,3-difluoro-4-[(2S)-2-methyloctyloxy]benzene.

[0272] 1 H NMR (400MHz, CDCl3) δppm 0.82-0.96(3H,m),1.02(3H,d,J=6.6Hz),1.09-1.88(36H,m),1.88-1.99(1H,m),3.74(1 H,m),3.83(1H,dd,J=9.0,5.8Hz),3.97(2H,t,J=6.5Hz),4.03-4.18(4H,m),6.61(2H,m).

[0273] 31 P NMR (162MHz, CDCl3) δppm 32.64.

[0274] Step 4: 11-[2,3-difluoro-4-[(2S)-2-methyloctyloxy]phenoxy]undecylphosphonic acid

[0275]

[0276] 11-[2,3-difluoro-4-[(2S)-2-methyloctyloxy]benzene was obtained by treating it with trimethylsilyl bromide as described in step 4 of Example 2 above, in the form of colorless crystals.

[0277] 1 H NMR(400MHz,CD3OD)δppm 0.88-0.98(3H,m),1.04(3H,d,J=6.7Hz),1.18-1.74(28H,m),1.74-1.83(2H,m),1.92(1H,m) ,3.79(1H,dd,J=9.2,6.8Hz), 3.86(1H,dd,J=9.0,5.8Hz), 4.00(2H,t,J=6.4Hz), 6.77(2H,m).

[0278] 19 F NMR (376MHz, CD3OD) δppm-159.71 (d, J = 17.7Hz), -159.80 (d, J = 17.7Hz).

[0279] 31 P NMR (162MHz, CD3OD) δppm 30.16.

[0280] Similar to the synthesis described above, the following compounds were obtained:

[0281]

[0282]

[0283]

[0284] Another object of the present invention is to provide a method for operating the above-described two-bit storage device.

[0285] In the proposed method, in order to switch the molecular layer (C) to a first resistive state, the bottom layer (A) is set to a first potential and the top layer (E) is set to a second potential, wherein the absolute value of the voltage between the bottom layer (A) and the top layer (E) is greater than a first switching voltage and the first potential is greater than the second potential. In order to switch the molecular layer (C) to a second resistive state, the bottom layer (A) is set to a third potential and the top layer (E) is set to a fourth potential, wherein the absolute value of the voltage between the bottom layer (A) and the top layer (E) is greater than a second switching voltage and the fourth potential is greater than the third potential.

[0286] The absolute values ​​of the first and second switching voltages can be the same so that the first and second switching voltages differ only in polarity.

[0287] Preferably, the state of the two-bit memory device is determined by applying an absolute value of a read voltage whose absolute value is less than that of the first and second switch voltages between the bottom layer (A) and the top layer (E) and measuring the resulting current.

[0288] Because the layered structure of a two-bit memory device has at least four different resistance states, the generated current reflects these different resistance states. Also, because the resistance difference between the two states of the molecular layer (C) and the two states of the top layer (E) differs by at least a factor of 10, each state of the molecular layer (C) and the top layer (E) can be identified by a single current measurement.

[0289] The first state of the molecular layer (C) and the top layer (E) can represent the high resistance state of their respective layers. Similarly, the second state of the molecular layer (C) and the top layer (E) can represent the low resistance state, or vice versa.

[0290] For the two-bit storage device according to the first embodiment, in order to switch the top layer (E) to the first resistive state, the bottom layer (A) is set to the fifth potential and the top layer (E) is set to the sixth potential, wherein the absolute value of the voltage between the bottom layer (A) and the top layer (E) is greater than the third switching voltage and the fifth potential is greater than the sixth potential, and in order to switch the top layer (E) to the second resistive state, the bottom layer (A) is set to the seventh potential and the top layer (E) is set to the eighth potential, wherein the absolute value of the voltage between the bottom layer (A) and the top layer (E) is greater than the fourth switching voltage and the eighth potential is greater than the seventh potential, and wherein the absolute values ​​of the third switching voltage and the fourth switching voltage are greater than the absolute values ​​of the first switching voltage and the second switching voltage, such that the states of the top layer (E) and the molecular layer (C) are simultaneously switched to their respective first or second resistive states, and if the molecular layer (C) is to be switched to a different state, an additional step of switching the molecular layer (C) is performed after the switching of the top layer (E).

[0291] In the two-bit memory device of the first embodiment, the magnetic switching of the top layer (E) is achieved by means of a spin-polarized current. To generate this spin-polarized current, a voltage is applied between the bottom layer (A) and the top layer (E). However, due to this voltage, an electric field is also applied to the molecular layer (C), potentially causing a switching of the resistance state of the molecular layer (C) similar to the dielectric switching. Therefore, after the state of the top layer (E) has been set using a third or fourth switching voltage with an absolute value higher than the absolute values ​​of the first and second switching voltages, a further switching step can be performed if necessary, wherein a first or second switching voltage is applied to set the resistance state of the molecular layer (C) after the resistance state of the top layer (E) has been set.

[0292] For the two-bit storage device according to the second embodiment, in order to switch the top layer (E) to a first resistive state, a first switching current is supplied to an electrical conductor arranged parallel to the top layer (E) by applying a ninth potential to a first electrical contact and a tenth potential to a second electrical contact, the first potential being greater than the second potential; and in order to switch the top layer (E) to a second resistive state, a second switching current is supplied to an electrical conductor arranged parallel to the top layer (E) by applying an eleventh potential to a first electrical contact and a twelfth potential to a second electrical contact, the twelfth potential being greater than the eleventh potential.

[0293] In the second embodiment of the two-bit storage device, the magnetic switching of the top layer (E) is achieved by means of an external magnetic field generated by an electrical conductor arranged parallel to the top layer (E). Since the respective switching voltages required to generate the respective switching currents do not apply an electric field to the molecular layer (C), the resistance state of the molecular layer (C) is not changed when the resistance state of the top layer (E) is switched.

[0294] When setting the state of a two-bit memory device, a voltage having at least the absolute value of its respective switching voltage can be applied in the form of a voltage pulse of predetermined duration, the duration of which is sufficient to change the respective state of the device.

[0295] The absolute values ​​of the first and second switching voltages may be the same. Similarly, the absolute values ​​of the third and fourth switching voltages may be the same. Furthermore, the absolute values ​​of the first and second switching currents may be the same.

[0296] This two-bit memory device has a magnetic state M and a dielectric state E, each of which can be set to "0" or "1" depending on their resistance state. In one example, to switch the molecular layer (C) to state 1... E Using a voltage +V E The first voltage pulse, and in order to switch to state 0 E Using a voltage –V E The second voltage pulse. To switch the top layer (E) to state 1. M Using a voltage +V M The third voltage pulse, and in order to switch to state 0 M Using a voltage –V M The fourth voltage pulse. Table 1 describes the voltage pulse sequence required for switching from each of the four possible configurations to any other possible configuration for the two-bit storage device of the first embodiment.

[0297]

[0298] (Table 1)

[0299] Another object of the present invention is to provide an electronic component comprising at least one of the aforementioned two-bit storage devices.

[0300] The electronic component can be configured as a storage device, particularly a non-volatile random access memory device, providing multiple storage cells, each storing 2 bits of information, and wherein each storage cell includes one of the two-bit storage devices. Additionally or alternatively, the electronic component can be configured as a logic device.

[0301] Preferably, the electronic component includes a cross array having word lines and bit lines and a plurality of two-bit memory devices, wherein the word lines are electrically connected to the bottom electrodes of the two-bit memory devices and the bit lines are connected to the top electrodes of the two-bit memory devices.

[0302] In such a cross-array configuration, bit lines and word lines are typically arranged such that they are rotated 90° relative to each other to form a cross shape. Preferably, two-bit memory devices are arranged at the intersections between the word lines and bit lines of the cross-array.

[0303] Preferably, a selection device is assigned to each of the plurality of binary memory devices. Transistors are particularly preferred as selection devices. Additionally or alternatively, each binary memory device may be coupled to a diode to reduce possible crosstalk between the devices. If transistors are used, the transistors are preferably configured as field-effect transistors (FETs). Brief description of the attached diagram

[0305] The attached image shows:

[0306] Figures 1a to 1d Different implementation schemes for the display layer structure.

[0307] Figure 2 This illustrates a first embodiment of a two-bit storage device, and

[0308] Figure 3 This illustrates a second embodiment of a two-bit storage device.

[0309] Figures 1a to 1d Four different implementations of the layer structure 10 of the two-bit storage device 1 are shown in [reference]. Figure 2 and 3 .

[0310] Figure 1a The first embodiment shows a layer structure 10, which consists of a bottom layer (A), a molecular layer (C), and a top layer (E) in that order. Each layer is in direct contact with the others.

[0311] The molecular layer (C) contains a chiral compound having at least a conformationally flexible molecular dipole moment. Due to its chiral structure, this chiral compound can act as a spin filter for electrons passing through the molecular layer (C). Because of the flexible conformation of this chiral compound, the polar functional groups of the molecule can change their orientation when an electric field is applied. The resistance to a current flowing from the bottom layer (A) through the molecular layer (C) into the top layer (E) depends on the orientation of the polar groups. Therefore, the state of the molecular layer (C) can be changed by applying an electric field.

[0312] The molecular layer (C) also acts as a spin injector and provides spin polarization current. Depending on the magnetization of the top layer (E), the spin polarization current flowing from the molecular layer (C) into the top layer (E) exhibits low or high resistance.

[0313] The top layer (E) is conductive and ferromagnetic. The top layer (E) can be magnetized. The state of the top layer (E) can be changed depending on the orientation of the magnetization.

[0314] In the first embodiment, the bottom layer (A) is preferably a substrate of a chiral compound that is a conductive material and also serves as a molecular layer (C). For example, a bottom layer made of conductive TiN can be used.

[0315] exist Figure 1bIn the second embodiment, the layer structure 10 is composed of a bottom layer (A), a molecular layer (C), an intermediate layer (D), and a top layer (E) in that order. Each layer is in direct contact with the others.

[0316] An additional intermediate layer (D) can be used to adjust the electrical properties of the layer structure and / or to protect the molecular layer (C). For example, depending on the electrical properties of the molecular layer (C), an intermediate layer (D) in the form of an electrically insulating layer may be required to reduce leakage current through the layer structure 10. The electrically insulating layer is, for example, an Al2O3 layer.

[0317] exist Figure 1c In the third embodiment, the layer structure 10 is composed of a bottom layer (A), an anchoring layer (B), a molecular layer (C), and a top layer (E) in that order. Each layer is in direct contact with the others.

[0318] The anchoring layer (B) acts as a substrate for the molecular layer (C) and does not need to be conductive. The anchoring layer (B) may be necessary for bonding the molecular layer (C). For example, a thin layer of Al₂O₃ can be used as the anchoring layer (B). The thin anchoring layer allows electrons to tunnel from the bottom layer (A) to the molecular layer (C) so that tunneling current can flow. In a preferred embodiment, the molecular layer (C) is directly bonded to the bottom layer (A) without the aid of an additional anchoring layer (B).

[0319] exist Figure 1d In the fourth embodiment, the layer structure 10 is composed of a bottom layer (A), an anchoring layer (B), a molecular layer (C), an intermediate layer (D), and a top layer (E) in that order. Each layer is in direct contact with the others.

[0320] Figure 2 A first embodiment of the two-bit storage device 1 is schematically shown, which includes a layer structure 10 embedded between a bottom electrode 14 and a top electrode 12.

[0321] Layer structure 10 as shown Figure 1a The configuration comprises, in this order, a bottom layer (A), a molecular layer (C), and a top layer (E). Alternatively, it can be used according to... Figures 1b to 1d The layer structure of the further implementation scheme 10.

[0322] The bottom electrode 14 is in direct contact with the bottom layer (A) and has an electrical contact 15 that is connected to a selection device 20, for example, configured as a transistor.

[0323] like Figure 2 The two-bit memory device 1 shown can be embedded in an electronic assembly containing a cross array. The top electrode 12 serves as the bit line 34 of the cross array. Furthermore, a select device 30 is connected to the word line 32 of the cross array. Using the select device 30, electrical contacts 15 can be connected to source lines 36 according to signals on word lines 32.

[0324] To read the state of the two-bit memory device 1, current flows from the source line 36 through the selector 30, the electrical contact 15, and the bottom electrode 14 to the layer structure 10 via the read path 40. The current flows through the bottom layer (A), the molecular layer (C), and the top layer (E) and finally flows into the top electrode 12 or the bit line 34.

[0325] The layer structure 10 has at least four different states for the resistance of the current flowing from the bottom layer (A) to the top layer (E), depending on the magnetization of the top layer (E) and the orientation of the conformational flexible dipole moment of the chiral compound in the molecular layer (C). Therefore, four different current levels can be detected, corresponding to four states of the two-bit memory device 1.

[0326] To set the state of the molecular layer (C), a voltage is applied along the dielectric write path 42, which is the same as the read path 40. Accordingly, respective switching voltages are applied via the top electrode 12 or the bit line 34 and the source line 36.

[0327] To set the state of the top layer (E), a spin-polarized current is applied by supplying current along a magnetic write path 44, the same as the read path 40 in the first embodiment. Accordingly, the current flows from the source line 36 through the select device 30, the electrical contact 15, and the bottom electrode 14 to the layer structure 10. The current flows through the bottom layer (A), the molecular layer (C), and the top layer (E) and finally flows into the top electrode 12 or the bit line 34. The current is spin-polarized by means of the molecular layer (C).

[0328] Figure 3 A second embodiment of the two-bit storage device 1 is schematically shown, which includes a layer structure 10 embedded between a bottom electrode 14 and a top electrode 12.

[0329] Layer structure 10 as shown Figure 1a The configuration comprises, in this order, a bottom layer (A), a molecular layer (C), and a top layer (E). Alternatively, it can be used according to... Figures 1b to 1d The layer structure of the further implementation scheme 10.

[0330] The bottom electrode 14 is in direct contact with the bottom layer (A) and has a first electrical contact 16, which is connected to a selection device 20, for example, configured as a transistor.

[0331] If correct Figure 2 As described in the two-bit memory device 1, the two-bit memory device 1 can be embedded in an electronic assembly containing a cross array. The top electrode 12 serves as the bit line 34 of the cross array. In addition, a select device 30 is connected to the word line 32 of the cross array. With the help of the select device 30, the electrical contact 15 can be connected to the source line 36 according to the signal on the word line 32.

[0332] To read the state of the two-bit memory device 1, the current is determined according to... Figure 2The first implementation scheme describes the flow of the reading path 40.

[0333] Also like Figure 2 The state of the molecular layer (C) is set by applying a voltage along the same dielectric write path 42 as the read path 40, as described in the first embodiment.

[0334] To set the state of the top layer (E), an external magnetic field is generated. For this purpose, a portion of the bottom electrode 14 serves as an electrical conductor 20 and applies current to this conductor 20. In order to apply current, the bottom electrode 14 includes a second electrical contact 18 in addition to the first electrical contact 16.

[0335] By applying a voltage difference between the first electrical contact 16 and the second electrical contact 18, a current is generated along the magnetic writing path 44, thereby generating a magnetic field for switching the top layer (E).

[0336] List of reference numerals

[0337] A bottom layer

[0338] B Anchoring Layer

[0339] C molecular layer

[0340] D Intermediate layer

[0341] E Top Floor

[0342] 1. Two-bit storage devices

[0343] 10-layer structure

[0344] 12 Top Electrode

[0345] 14 Bottom Electrode

[0346] 16 First electrical contact

[0347] 18 Second electrical contact

[0348] 20 Electrical conductors

[0349] 30 Select Devices

[0350] 32-line

[0351] 34-bit line

[0352] 36 source lines

[0353] 40 Read Path

[0354] 42 Write path dielectric state

[0355] 44 Write path magnetic state

Claims

1. A two-bit storage device (1) having a layered structure (10), the layered structure (10) comprising, in this order, a binary storage device (1) having a layered structure (10 ... Bottom layer (A), Molecular layer (C), which contains a chiral compound having at least one polar functional group, and Top layer (E), The top layer (E) is both conductive and ferromagnetic. The chiral compound described therein acts as a spin filter for electrons passing through the molecular layer (C), and the chiral compound has a flexible conformation and a conformationally flexible molecular dipole moment. The layer structure (10) has at least four different states of resistance to current flowing from the bottom layer (A) to the top layer (E), depending on the magnetization of the top layer (E) and the orientation of the conformational flexible dipole moment of the chiral compound in the molecular layer (C). The chiral compound is selected from compounds of the following formula. in R 1 This refers to straight-chain or branched racemic or branched non-racemic alkyl or alkoxy groups, each having a maximum of 20 carbon atoms, wherein one or more CH2 groups among these groups can be independently separated by -C. C-, -CH=CH-, , , , , , , -O-, -S-, -CF2O-, -OCF2-, -CO-O-, -O-CO-, -SiR 0 R 00 -、-NH-、-NR 0 - or -SO2- is substituted in such a way that the O atoms are not directly connected to each other, and one or more of the H atoms can be replaced by halogens, CN, SCN, or SF5. R 1C This refers to straight-chain or branched racemic or branched non-racemic alkyl or alkoxy groups, each having a maximum of 20 carbon atoms, wherein one or more CH2 groups among these groups can be independently separated by -C. C-, -CH=CH-, , , , , , -O-, -S-, -CF2O-, -OCF2-, -CO-O-, -O-CO-, -SiR 0 R 00 -、-NH-、-NR 0 - or -SO2- is replaced by O atoms that are not directly connected to each other, and one or more H atoms can be replaced by halogens, CN, SCN, or SF5, and alternatively refers to the D group. 1 -Z D , Z D With Z 1 Z 2 and Z 3 One meaning may refer to a spacer group. Z 1 Z 2 Z 3 Each occurrence may represent a single bond, -CF2O-, -OCF2-, -CF2S-, -SCF2-, -CH2O-, -OCH2-, -C(O)O-, -OC(O)-, -C(O)S-, -SC(O)-, or -(CH2). n1 -、-(CF2) n2 -, -CF2-CH2-, -CH2-CF2-, -CH=CH-, -CF=CF-, -CF=CH-, -CH=CF-, -(CH2) n3 O-, -O(CH2) n4 -、-C C-, -O-, -S-, -CH=N-, -N=CH-, -N=N-, -N=N(O)-, -N(O)=N- or -N=CC=N-, n1, n2, n3, and n4 are the same or different from 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10. Z L This refers to -O-, -S-, -CH2-, -C(O)-, -CF2-, -CHF-, and -C(R). x )2-, -S(O)- or -SO2-, wherein the group -CHF- or the asymmetrically substituted group -C(R) x )2- is either racemic or non-racemic. R 0 R 00 The same or different refer to alkyl or alkoxy groups having 1 to 15 carbon atoms, wherein, Furthermore, one or more H atoms can be replaced by halogens. R x Each time it appears, it may represent H or a straight-chain or branched alkyl group having 1 to 6 carbon atoms, either the same or different. D 1 This refers to an adamantane group in which one or more H atoms can be replaced by F, or optionally fluorinated alkyl, alkenyl, or alkoxy groups having up to 12 C atoms in each case. A 1 A 2 A 3 Each occurrence may be identical or different, representing an aromatic, heteroaromatic, alicyclic, or heteroaliphatic ring having 4 to 25 ring atoms. It may also contain fused rings and may be mono- or poly-substituted by Y. A 2C It refers to an aromatic or heteroaromatic ring with 5 to 25 ring atoms, which may also contain fused rings and can be Y-shaped. C Single or multiple substitutions, Y, in each occurrence, may refer to F, Cl, CN, SCN, SF5, or a straight-chain or branched alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy, or alkoxycarbonyloxy group having 1 to 12 carbon atoms, optionally fluorinated in each case. Y C Each occurrence may be identical or different and may represent F, Cl, CN, SCN, SF5, or a straight-chain or branched alkyl, alkoxy, alkyl carbonyl, alkoxy carbonyl, alkyl carbonyloxy, or alkoxy carbonyloxy, or a cycloalkyl or alkylcycloalkyl, each having 1 to 12 carbon atoms, optionally fluorinated in each case. L 1 To L 3 Each of these can be independently represented as F, Cl, Br, I, CN, SF5, CF3, or OCF3, where L 3 H can also be used as an alternative representation. Sp A This refers to spacer groups or single bonds. Sp refers to a chiral spacer group. G represents -OH, -CH(CH2OH)2, -C(CH2OH)3, -SH, -SO2OH, -OP(O)(OH)2, -PO(OH)2, -C(OH)(PO(OH)2)2, -COOH, -Si(OR x )3 or -SiCl3, -SO2OR V , -OP(O)(OR V )2, -PO(OR V )2, -C(OH)(PO(OR V )2)2, -COOR V or -Si(OR V )3, R V It refers to secondary or tertiary alkyl groups having 1 to 20 carbon atoms, and r and s are either 0, 1, or 2 each time they appear. Where R in equation IA 1 and Sp A At least one of them is chiral, and R of IC 1C and Z L At least one of them is chiral. And among them B 1 It is polar.

2. The two-bit storage device (1) according to claim 1, characterized in that... Chiral compounds in the molecular layer (C) bind to the underlying layer (A) or Its features An anchoring layer (B) for binding the chiral compound to the molecular layer (C) is arranged between the bottom layer (A) and the molecular layer (C), and the chiral compound of the molecular layer (C) is bound to the anchoring layer (B).

3. The two-bit storage device (1) according to claim 1, characterized in that... The intermediate layer (D) is arranged between the molecular layer (C) and the top layer (E).

4. The two-bit storage device (1) according to claim 2, characterized in that... The intermediate layer (D) is arranged between the molecular layer (C) and the top layer (E).

5. The two-bit storage device (1) according to claim 2, characterized in that... The materials of the anchoring layer (B) and / or the intermediate layer (D) are selected from Al2O3, ZrO2, HfO2, TiO2, SiO2, ITO, AZO, IGZO, ZnO, MgO and combinations thereof.

6. The two-bit storage device (1) according to claim 3, characterized in that... The materials of the anchoring layer (B) and / or the intermediate layer (D) are selected from Al2O3, ZrO2, HfO2, TiO2, SiO2, ITO, AZO, IGZO, ZnO, MgO and combinations thereof.

7. The two-bit storage device (1) according to any one of claims 1 to 6, characterized in that... The material of the bottom layer (A) is selected from doped Si and Al, W, Mo, Ru, Ag, Au, TiN, TaN and combinations thereof.

8. The two-bit storage device (1) according to any one of claims 1 to 6, characterized in that... The material of the top layer (E) is selected from Ni, Co, Fe, NiFe, CoFeB, CoFe, GdFe, TbFeCo, GdFeCo and combinations thereof.

9. The two-bit storage device (1) according to claim 7, characterized in that... The material of the top layer (E) is selected from Ni, Co, Fe, NiFe, CoFeB, CoFe, GdFe, TbFeCo, GdFeCo and combinations thereof.

10. The two-bit storage device (1) according to any one of claims 1 to 6, characterized in that... A molecular layer (C) is a self-assembled monolayer containing molecules of a chiral compound.

11. The two-bit storage device (1) according to claim 9, characterized in that... A molecular layer (C) is a self-assembled monolayer containing molecules of a chiral compound.

12. The two-bit storage device (1) according to any one of claims 1 to 6, characterized in that... The quotient of the difference between the resistances of the two states of the molecular layer (C) and the difference between the resistances of the two states of the top layer (E) is in the range of 10 to 10,000.

13. The two-bit storage device (1) according to claim 11, characterized in that... The quotient of the difference between the resistances of the two states of the molecular layer (C) and the difference between the resistances of the two states of the top layer (E) is in the range of 10 to 10,000.

14. The two-bit storage device (1) according to any one of claims 1 to 6, characterized in that... Configure the bottom layer (A) as the bottom electrode (14) or connect it to the bottom electrode (14), and connect the top layer (E) to the top electrode (12), and To switch the molecular layer (C) to a first resistive state or a second resistive state, a first or second switching voltage is applied between the bottom layer (A) and the top layer (E), and To switch the top layer (E) to either the first or second resistance state, a third or fourth switching voltage is applied between the bottom layer (A) and the top layer (E). The absolute values ​​of the third and fourth switching voltages are at least twice the absolute values ​​of the first and second switching voltages.

15. The two-bit storage device (1) according to claim 13, characterized in that... Configure the bottom layer (A) as the bottom electrode (14) or connect it to the bottom electrode (14), and connect the top layer (E) to the top electrode (12), and To switch the molecular layer (C) to a first resistive state or a second resistive state, a first or second switching voltage is applied between the bottom layer (A) and the top layer (E), and To switch the top layer (E) to either the first or second resistance state, a third or fourth switching voltage is applied between the bottom layer (A) and the top layer (E). The absolute values ​​of the third and fourth switching voltages are at least twice the absolute values ​​of the first and second switching voltages.

16. The two-bit storage device (1) according to any one of claims 1 to 6, characterized in that... The bottom layer (A) is configured as the bottom electrode (14) or in contact with the bottom electrode (14), and The bottom electrode (14) contacts the first electrical contact (16) and the second electrical contact (18) to form an electrical conductor (20) arranged parallel to the top layer (E). The first electrical contact (16) and the second electrical contact (18) are arranged such that when a voltage is applied between the first electrical contact (16) and the second electrical contact (18), current flows through the electrical conductor (20).

17. The two-bit storage device (1) according to claim 15, characterized in that... The bottom layer (A) is configured as the bottom electrode (14) or in contact with the bottom electrode (14), and The bottom electrode (14) contacts the first electrical contact (16) and the second electrical contact (18) to form an electrical conductor (20) arranged parallel to the top layer (E). The first electrical contact (16) and the second electrical contact (18) are arranged such that when a voltage is applied between the first electrical contact (16) and the second electrical contact (18), current flows through the electrical conductor (20).

18. The two-bit storage device (1) according to any one of claims 1 to 6, characterized in that... The adamantane groups are derived from lower adamantane groups.

19. The two-bit storage device (1) according to any one of claims 1 to 6, characterized in that... The adamantane group is selected from adamantyl, didamantyl, and tridamantyl.

20. The two-bit storage device (1) according to any one of claims 1 to 6, characterized in that... Y may represent F or Cl in the same or different ways each time it appears.

21. The two-bit storage device (1) according to any one of claims 1 to 6, characterized in that... Y C Each time it appears, it may be the same or different representation of methyl, ethyl, isopropyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, trifluoromethyl, methoxy, or trifluoromethoxy.

22. The two-bit storage device (1) according to any one of claims 1 to 6, characterized in that... L 1 To L 3 They can be represented independently as CF3, Cl, or F.

23. The two-bit storage device (1) according to claim 1, characterized in that... D 1 It means or .

24. A method for operating the two-bit storage device (1) according to any one of claims 1 to 23, characterized in that... To switch the molecular layer (C) to a first resistive state, the bottom layer (A) is set to a first potential and the top layer (E) is set to a second potential, wherein the absolute value of the voltage between the bottom layer (A) and the top layer (E) is greater than a first switching voltage and the first potential is greater than the second potential. In order to switch the molecular layer (C) to the second resistive state, the bottom layer (A) is set to the third potential and the top layer (E) is set to the fourth potential, wherein the absolute value of the voltage between the bottom layer (A) and the top layer (E) is greater than the second switching voltage and the fourth potential is greater than the third potential.

25. The method of operating a two-bit storage device (1) according to claim 24, characterized in that... The state of the two-bit memory device (1) is determined by applying a read voltage whose absolute value is less than the first and second switch voltages between the bottom layer (A) and the top layer (E) and measuring the resulting current.

26. The method of operating a two-bit storage device (1) according to claim 24, characterized in that... For the two-bit storage device (1) according to claim 14, To switch the top layer (E) to the first resistive state, the bottom layer (A) is set to the fifth potential and the top layer (E) is set to the sixth potential, wherein the absolute value of the voltage between the bottom layer (A) and the top layer (E) is greater than the third switching voltage and the fifth potential is greater than the sixth potential. To switch the top layer (E) to the second resistive state, the bottom layer (A) is set to the seventh potential and the top layer (E) is set to the eighth potential, wherein the absolute value of the voltage between the bottom layer (A) and the top layer (E) is greater than the fourth switching voltage and the eighth potential is greater than the seventh potential. Furthermore, the absolute values ​​of the third and fourth switching voltages are greater than the absolute values ​​of the first and second switching voltages, such that the states of the top layer (E) and the molecular layer (C) simultaneously switch to their respective first or second resistance states. If the molecular layer (C) needs to switch to a different state, an additional step of switching the molecular layer (C) is performed after the switching of the top layer (E).

27. The method of operating a two-bit storage device (1) according to claim 25, characterized in that... For the two-bit storage device (1) according to claim 14, To switch the top layer (E) to the first resistive state, the bottom layer (A) is set to the fifth potential and the top layer (E) is set to the sixth potential, wherein the absolute value of the voltage between the bottom layer (A) and the top layer (E) is greater than the third switching voltage and the fifth potential is greater than the sixth potential. To switch the top layer (E) to the second resistive state, the bottom layer (A) is set to the seventh potential and the top layer (E) is set to the eighth potential, wherein the absolute value of the voltage between the bottom layer (A) and the top layer (E) is greater than the fourth switching voltage and the eighth potential is greater than the seventh potential. Furthermore, the absolute values ​​of the third and fourth switching voltages are greater than the absolute values ​​of the first and second switching voltages, such that the states of the top layer (E) and the molecular layer (C) simultaneously switch to their respective first or second resistance states. If the molecular layer (C) needs to switch to a different state, an additional step of switching the molecular layer (C) is performed after the switching of the top layer (E).

28. The method of operating a two-bit storage device (1) according to claim 24, characterized in that... For the device (1) according to claim 16, To switch the top layer (E) to the first resistive state, a first switching current is supplied to an electrical conductor arranged parallel to the top layer (E) by applying a ninth potential to the first electrical contact and a tenth potential to the second electrical contact. The first potential is greater than the second potential. In order to switch the top layer (E) to the second resistive state, a second switching current is supplied to an electrical conductor arranged parallel to the top layer (E) by applying an eleventh potential to the first electrical contact and a twelfth potential to the second electrical contact, the twelfth potential being greater than the eleventh potential.

29. The method of operating a two-bit storage device (1) according to claim 25, characterized in that... For the device (1) according to claim 16, To switch the top layer (E) to the first resistive state, a first switching current is supplied to an electrical conductor arranged parallel to the top layer (E) by applying a ninth potential to the first electrical contact and a tenth potential to the second electrical contact. The first potential is greater than the second potential. In order to switch the top layer (E) to the second resistive state, a second switching current is supplied to an electrical conductor arranged parallel to the top layer (E) by applying an eleventh potential to the first electrical contact and a twelfth potential to the second electrical contact, the twelfth potential being greater than the eleventh potential.

30. An electronic component comprising at least one two-bit storage device (1) according to any one of claims 1 to 23.

31. The electronic component according to claim 30, characterized in that... The electronic component includes a cross array having word lines (32) and bit lines (34) and a plurality of two-bit memory devices (1), wherein the word lines (32) are electrically connected to the bottom electrode (14) of the two-bit memory device (1) and the bit lines (34) are connected to the top electrode (12) of the two-bit memory device (1).

32. The electronic component of claim 31, wherein a selection device (30) is assigned to each of the plurality of binary storage devices (1).

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