Electronic switching device

Abstract

To provide new compounds for the fabrication of improved electronic components comprising a molecular layer bonded to a first electrode, suitable for use in memristive devices, which bring improvements with respect to improved endurance.SOLUTION: The present invention relates to an electronic switching device, in particular to tunnel junctions, comprising an organic molecular layer for use in memory, sensors, field-effect transistors or Josephson junctions. More particularly, the invention is included in the field of random access non-volatile memristive memories (RRAM). Further, aspects of the present invention relate to compounds represented by following formula I for use in the molecular layer. The present invention further relates to the use of the molecular layer and to processes for the production and operation of the electronic switching element and components based thereon.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to electronic switching devices, particularly tunnel junctions, comprising organic molecular layers for use in memories, sensors, field-effect transistors, or Josephson junctions. More particularly, the present invention is encompassed in the field of random-access nonvolatile memristor memories (RRAMs). Further aspects of the present invention relate to compounds for use in molecular layers, uses of the molecular layers, and processes for the manufacture and operation of electronic switching elements and components based thereon. [Background technology]

[0002] Tunnel junctions are used for many applications in the electronics industry, ranging from superconducting Josephson junctions to tunnel diodes. They require extremely thin dielectric materials as insulators. One of the most cost-effective ways to create such insulating layers with single-digit nanometer thicknesses is by using self-assembled monolayers (SAMs).

[0003] Computer technology requires storage media that allow fast writing and reading access of the stored information. Solid-state or semiconductor memories allow particularly fast and reliable storage media to be achieved, since they do not require any moving parts. Currently, use is mainly made of dynamic random access memories (DRAMs). DRAMs allow fast access to the stored information, but this information must be updated regularly, meaning that the stored information is lost when the power supply is switched off.

[0004] The prior art also discloses non-volatile semiconductor memories, such as flash memory or magnetoresistive random access memory (MRAM), that retain information even after the power supply is switched off. The drawback of flash memory is that write access occurs relatively slowly and the memory cells of flash memory cannot be erased indefinitely. The lifespan of flash memory is usually limited to a maximum of one million read / write cycles. MRAM can be used in a manner similar to DRAM and has a long lifespan, but has not been able to establish itself due to the difficulty of the manufacturing process.

[0005] Another alternative is memristor-based memory. The term memristor is a contraction of "memory" and "resistor" and refers to a component whose electrical resistance can be reproducibly changed between high and low resistance. Each state (high or low resistance) is maintained without a voltage supply, meaning that nonvolatile memory can be achieved by memristors. Memristor crossbar arrays may be used in a variety of applications, including nonvolatile solid-state memory, programmable logic, signal processing, control systems, pattern recognition, and other applications. A memristor crossbar array includes multiple row lines, multiple column lines that intersect the row lines to form multiple junctions, and multiple resistive memory devices coupled between the row and column lines at the junctions.

[0006] For example, WO 2012 / 127542 A1 and US 2014 / 008601 A1 disclose organic molecular memory devices having two electrodes and an active region disposed between the two electrodes. The active region comprises a molecular layer of conductive aromatic alkynes, the conductivity of which can be changed under the influence of an electric field. A similar device based on redox-active pyridinium compounds is proposed in US 2005 / 0099209 A1.

[0007] Known memories based on changes in conductivity or resistance have the drawback that the free radical intermediates formed by passing an electric current through the molecules of the molecular layer are in principle susceptible to degradation processes, which have a negative impact on the lifetime of the component.

[0008] In WO 2018 / 007337 A2, an improved switching layer is described that utilizes a non-oxidatively active molecular layer comprising dipolar compounds linked to a substrate via aliphatic spacer groups, where the compounds are reversibly switched by application of an electric field that causes orientation of the molecular dipoles and thus enables low and high resistance states depending on the respective orientation of the molecules.

[0009] To obtain electrically switchable tunnel junctions from organic compounds with structurally flexible dipoles, a molecular layer sandwiched between two conductive electrodes is desired. Deposition of this molecular layer onto the electrodes is achieved either by spin coating or by dip coating from an organic solvent. The basic principles of the resulting memory device are described in WO 2016 / 110301 A1 and WO 2018 / 007337 A2.

[0010] It is desirable for information storage devices using electrically switchable tunnel barriers made from self-assembled bipolar monolayers to have long retention times of selected states, even at high temperatures, for example, up to 85° C. Long retention times enable memory devices that require fewer refresh cycles. There remains a need in the art for devices with long retention times.

[0011] Furthermore, the information storage device includes: 15 It is desirable for the material to have a durability of at least 100 read / write cycles. To achieve such extremely high reliability, it is necessary to reduce the number and mobility of ionic impurities within the molecular layer. In particular, ion migration can cause reliability problems such as reduced durability, high cycle-to-cycle variations in electrical properties, and poor device-to-device reproducibility of electrical performance.

[0012] It is an object of the present invention to provide novel compounds for the fabrication of improved electronic components comprising a molecular layer attached to a first electrode, suitable for example for use in memristor devices, which do not have the drawbacks mentioned above and which offer improvements, in particular with regard to improved durability. Summary of the Invention

[0013] To achieve this goal, compounds of formula I are provided, [ka] During the ceremony T is the following group: a) linear or branched alkyl or alkoxy, each having 1 to 20 C atoms, in which one or more CH groups in the radical are independently -C≡C-, -CH=CH-, [ka] -O-, -S-, -CF2O-, -OCF2-, -CO-O-, -O-CO-, -SiR 0 R 00 -, -NH-, -NR 0 - or -SO2-, each replaced by O atoms in such a way that they are not directly linked to one another, and wherein one or more H atoms may be replaced by halogen, CN, SCN or SF5, b) at least one -CH2- group is -O-, -S-, -S(O)-, -SO2-, or -NR x -or-N(O)R x a 3- to 10-membered saturated or partially unsaturated aliphatic ring, wherein at least one -CH= group is replaced by - or at least one -CH= group is replaced by -N=; c) diamondoid radicals, preferably derived from lower diamondoids, very preferably lower diamondoids selected from the group consisting of adamantyl, diamantyl and triamantyl, in which one or more H atoms may be replaced by F, in each case optionally fluorinated, alkyl, alkenyl or alkoxy having up to 12 C atoms, in particular [ka] is selected from the group of radicals consisting of: Z T , Z 1 , Z 2 , and Z 4 represents, in each occurrence, identically or differently, a single bond, -CF2O-, -OCF2-, -CF2S-, -SCF2-, -C2O-, -OCH2-, -C(O)O-, -OC(O)-, -C(O)S-, -SC(O)-, -(CH2) n1 -, -(CF2) n2 -, -CF2CH2-, -CH2CF2-, -CH=CH-, -CF=CF-, -CF=CH-, -CH=CF-, -(CH2) n3 O-, -O(CH2) n4 represents -, -C≡C-, -O-, -S-, -CH=N-, -N=CH-, -N=N-, -N=N(O)-, -N(O)=N- or -N=CC=N-, wherein n1, n2, n3, and n4, whether identical or different, are 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10; Z 3 -O-, -S-, -CH2-, -C(O)-, -CF2-, -CHF-, -C(R x )2-, -S(O)- or -SO2-; [ka] represents, in each occurrence, identically or differently, an aromatic, heteroaromatic, alicyclic, or heteroaliphatic ring having 4 to 25 ring atoms, which may also contain fused rings and which may be monosubstituted by X, or R Lmay be mono- or polysubstituted by [ka] represents an aromatic or heteroaromatic ring having 5 to 25 ring atoms, which may also contain fused rings and which may be monosubstituted by X, or R c may be mono- or polysubstituted by [ka] teeth, [ka] represents X represents F, Cl, Br, I, CN, SF, CF, OCF, or OCHF, preferably Cl or F, very preferably F; R L represents, identically or differently, in each occurrence, H, alkyl having 1 to 6 C atoms, alkenyl having 2 to 6 C atoms or alkoxy having 1 to 5 C atoms, preferably H or alkyl having 1 to 4 C atoms, very preferably H, methyl or ethyl, R C represents, in each occurrence, identically or differently, straight-chain or branched, in each case optionally fluorinated alkyl, alkoxy, alkylthio, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy having 1 to 12 C atoms or cycloalkyl or alkylcycloalkyl, each having 3 to 12 C atoms, preferably methyl, ethyl, isopropyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, trifluoromethyl, methoxy, trifluoromethoxy or trifluoromethylthio, Sp represents a spacer group or a single bond; R 0 , R 00 , R x represents a linear or branched alkyl having 1 to 6 carbon atoms, G is -OH, -SH, -SO2OH, -OP(O)(OH)2, -PO(OH)2, -C(OH)(PO(OH)2)2, -COOH, -Si(OR x )3, -SiCl3, -CH=CH2, -POCl2, -COH(PO(OH)2)2, -CO(NHOH), -CO(NR 0 -OH), -Si(NMe2)3; or linear or branched alkyl having 1 to 12 carbon atoms, in which one, two or three non-geminal H atoms are replaced by OH; or -OC(O)-OR V , -OC(O)-Si(OR x )3, PO(OR V )2, SO2OR V represents a group selected from R V represents a linear or branched alkyl having 1 to 12 carbon atoms, and r, s, t and u, identically or differently, are 0, 1 or 2, where r+s+t+u=0, 1, 2, 3 or 4.

[0014] According to another aspect of the invention, in this order: a first electrode; molecular layer, and a second electrode, wherein the molecular layer is formed essentially of one or more, preferably one, compound of formula I as defined above and below.

[0015] In one embodiment, the molecular layer is attached to the first electrode. In a preferred embodiment, an intermediate film is provided between the first electrode and the molecular layer. In this case, the molecular layer is attached to the intermediate film, and in other words, the first electrode and the intermediate film can function as the first electrode.

[0016] The invention further relates to a process for the manufacture of a switching device according to the invention, comprising at least the following steps: i. Fabricating a first electrode having a surface; ii. Deposition, on the surface of the first electrode, of a molecular layer comprising one or more compounds selected from the group of compounds of formula I defined above; iii. Application of a second electrode.

[0017] The present invention further relates to a method for operating an electronic component according to the present invention, characterized in that a switching device of the electronic component is switched to a high electrical resistance state by setting a corresponding first electrode to a first potential and a corresponding second electrode to a second potential, wherein a value of the voltage between the two electrodes is greater than a first switching voltage and the first potential is greater than the second potential; a switching device of the electronic component is switched to a low electrical resistance state by setting the corresponding first electrode to a third potential and the corresponding second electrode to a fourth potential, wherein a value of the voltage between the two electrodes is greater than the second switching voltage and the fourth potential is greater than the third potential; and a state of the switching device is determined by applying a read voltage between the corresponding electrodes, the read voltage being smaller than the first and second switching voltages, and measuring the current flowing.

[0018] According to another aspect of the present invention, there is provided an electronic component, wherein the component is a memristor crossbar array comprising a number of switching devices according to the present invention. The crossbar array can be integrated into a three-dimensional array of cells comprising a stack of two or more crossbar arrays. Such a configuration is known as a 3D crosspoint or 3D X-point memory device.

[0019] The present invention further relates to the use of a molecular layer obtained from one or more compounds as indicated in claim 1 in a memristor electronic component. The resulting devices can be used in memories, sensors, field effect transistors or Josephson junctions, preferably in resistive memory devices. The invention further relates to the use of the switching device in a memory, a sensor, a field effect transistor or a Josephson junction.

[0020] The switching device according to the invention is suitable for use in electronic components, in particular in memories, sensors, field effect transistors or Josephson junctions, very especially in memristor components such as memristor crossbar arrays exhibiting the advantageous properties indicated above.

[0021] The compounds of formula I according to the present invention enable switching devices that are distinguished by improved retention by several orders of magnitude compared to the state of the art. Tunnel junctions based on SAM precursors of formula I exhibit significantly higher current densities in their current-voltage characteristics, enabling faster read operations and higher integration densities.

[0022] The switching voltage of the switching device according to the invention is advantageously low, and the switching device exhibits high reliability and durability. Furthermore, the memory window is advantageously large, an improvement over devices known from the prior art.

[0023] The memory devices based on the compounds according to the present invention exhibit less noisy current-voltage (IV) characteristics, allowing faster read or write speeds. Compared to the highly fluorinated compounds of the prior art, the reduced polarity of the compounds according to the present invention reduces intermolecular electrostatic interactions and therefore increases the write speed in particular. The endurance is also significantly improved.

[0024] The electrode materials that can be used in the devices according to the invention are highly compatible with semiconductor industry devices and fabrication processes, and are surprisingly well suited to the formation of stable, homogeneous molecular monolayers. [Brief explanation of the drawings]

[0025] [Figure 1] Figure 1A shows a schematic representation of the layer structure of a first embodiment of an electronic switching device, and Figure 1B shows a schematic representation of the layer structure of a second embodiment of an electronic switching device according to the present invention.

[0026] [Figure 2] FIG. 2 shows the current-voltage curve of an electronic switching device according to the invention. [Figure 3] FIG. 3 shows the current-voltage curve of the electronic reference device without the molecular monolayer.

[0027] In claim 7, the expression "essentially formed from" is understood to mean that among the compounds used to form the molecular layer, certain further compounds may be present, i.e., compounds that do not significantly affect the essential properties of the molecular layer. As used herein, the term "RRAM" or "resistive memory device" is understood to mean a memory device that uses a molecular switching layer whose resistance can be controlled by applying a voltage.

[0028] The low resistance state (LRS) or ON state of a resistance memory device is understood to mean a state in which the resistance memory device has a low electrical resistance. The high resistance state (HRS) or OFF state of a resistance memory device is understood to mean a state in which the resistance memory device has a high resistance. A memory window is understood to mean an interval of resistance values ​​having a lower bound and an upper bound.

[0029] A state with a resistance value below the lower limit of this interval is considered to be an ON state. A state with a resistance value higher than the upper limit of this interval is considered to be an OFF state.

[0030] The term "diamondoid" refers to substituted and unsubstituted caged compounds of the adamantane series, including adamantane, diamantane, triamantane, tetramantane, pentamantane, hexamantane, heptamantane, octamantane, and the like, including all isomers and stereoisomers thereof. These compounds have a "diamondoid" topology, meaning that the arrangement of carbon atoms superimposes a fragment of a face-centered cubic diamond lattice. Substituted diamondoids from the first series preferably have one to four independently selected alkyl or alkoxy substituents.

[0031] Diamondoids, as defined herein, include "lower diamondoids" and "higher diamondoids," as well as mixtures of any combination of lower and higher diamondoids. The term "lower diamondoids" refers to any and / or all of adamantane, diamantane, and triamantane, and unsubstituted and substituted derivatives of adamantane, diamantane, and triamantane. These lower diamond building blocks do not exhibit isomerism or chirality and are easily synthesized, distinguishing them from "higher diamonds." The term "higher diamondoid" refers to any and / or all substituted and unsubstituted tetramantane components; any and / or all substituted and unsubstituted pentamantane components; any and / or all substituted and unsubstituted hexamantane components; any and / or all substituted and unsubstituted heptamantane components; any and / or all substituted and unsubstituted octamantane components; and mixtures of the above, as well as isomers and stereoisomers of tetramantane, pentamantane, hexamantane, heptamantane, and octamantane. The chemistry of adamantane is reviewed in Fort, Jr. et al., "Adamantane: Consequences of the Diamondoid Structure," Chem. Rev., vol. 64, pp. 277-300 (1964). Adamantane is the smallest member of the diamondoid series and may be considered as a subunit of a single cage crystal. Diamantane contains two subunits, triamantane three, tetramantane four, etc. While adamantane, diamantane, and triamantane have only one isomer, tetramantane has four isomers (two of which are enantiomeric pairs), i.e., four different ways or arrangements of the four amantane subunits are possible. With each higher member of the diamondoid series, such as pentamantane, hexamantane, heptamantane, and octamantane, the number of possible isomers increases nonlinearly. Commercially available adamantane has been extensively studied.Research is being conducted in many areas, including 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 and application of functionalized diamondoids to form large-area SAMs on silver and gold surfaces. KT Narasimha et al., Nature Nanotechnology 11, March 2016, pp. 267-273, describe how diamondoid monolayers effectively impart enhanced field emission properties to metal surfaces by significantly reducing the work function of the metal.

[0032] As used herein, an anchoring group is a functional group that allows a compound to adsorb or bind to the surface of a substrate or electrode by physical adsorption, chemisorption, or chemical reaction, which involves converting a precursor of the anchoring group in situ, for example, at the surface of the substrate or electrode.

[0033] In the sense of the present invention, a spacer group is a flexible chain between the dipolar moiety and the anchor group, which creates a separation between these moieties and, at the same time, its flexibility improves the mobility of the dipolar moiety after binding to the substrate. The spacer group can be branched or straight-chain. Chiral spacers are branched and optically active and non-racemic.

[0034] In this specification, alkyl is linear or branched and has 1 to 15 C atoms, preferably linear, and, unless otherwise indicated, has 1, 2, 3, 4, 5, 6 or 7 C atoms and is accordingly preferably methyl, ethyl, propyl, butyl, pentyl, hexyl or heptyl.

[0035] In this specification, an alkoxy radical is linear or branched and contains 1 to 15 C atoms. It is preferably linear and, unless otherwise indicated, has 1, 2, 3, 4, 5, 6 or 7 C atoms and is accordingly preferably methoxy, ethoxy, propoxy, butoxy, pentoxy, hexoxy or heptoxy.

[0036] In this specification, the alkenyl radical is preferably an alkenyl radical having 2 to 15 carbon atoms, is linear or branched, and contains at least one C-C double bond. It is preferably linear and has 2 to 7 carbon atoms. Accordingly, 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, hept-1-, -2-, -3-, -4-, -5- or -6-enyl. If two carbon atoms of the C-C double bond are substituted, the alkenyl radical can be in the form of an E and / or Z isomer (trans / cis). Generally, the respective E isomer is preferred. Of the alkenyl radicals, prop-2-enyl, but-2- and -3-enyl, and pent-3- and -4-enyl are especially preferred.

[0037] In the present specification, alkynyl is understood to mean an alkynyl radical having 2 to 15 C atoms, which is linear or branched and contains at least one C-C triple bond. 1- and 2-propynyl, and 1-, 2- and 3-butynyl are preferred.

[0038] The compounds of general formula I are prepared by methods known per se and under reaction conditions known and suitable for said reactions, as described in the literature (e.g. in standard works such as Houben-Weyl, Methoden der organischen Chemie [Methods of Organic Chemistry], Georg-Thieme-Verlag, Stuttgart).

[0039] A preferred synthesis route is similar to the synthesis of similar compounds described in WO 2018 / 007337 A2, WO 2019 / 238649 A2, WO 2020 / 225270 A2, WO 2020 / 225398 A2, WO 2021 / 078699 A2, WO 2021 / 078714 A2 and WO 2021 / 083934 A2. Use here can be made in variants that are known and described in the literature and are exemplified below by examples.

[0040] In Formula I, preferred aryl groups are derived, for example, from the parent structures benzene, naphthalene, tetrahydronaphthalene, 9,10-dihydrophenanthrene, fluorene, indene, and indane.

[0041] In formula I, preferred heteroaryl groups are five-membered rings such as, for example, 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, six-membered rings such as, for example, pyridine, pyridazine, pyrimidine, pyrazine, 1,3,5-triazine, 1,2,4-triazine and 1,2,3-tolidine, or , indole, isoindole, indolizine, indazole, benzimidazole, benzotriazole, purine, naphthymidazole, benzoxazole, naphthoxazole, benzothiazole, benzofuran, isobenzofuran, dibenzofuran, thieno[2,3b]-thiophene, thieno[3,2b]thiophene, dithienothiophene, isobenzothiophene, dibenzothiophene, benzothiadiazothiophene, 2H-chromene (2H-1-benzopyran), 4H-chromene (4H-1-benzopyran), and coumarin (2H-chromen-2-one), or a combination of these groups.

[0042] In Formula I, preferred cycloaliphatics 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.

[0043] Preferred spacer groups Sp are selected from the formula Sp'-X', such that the radical G-Sp- of formula I corresponds to the formula G-Sp'-X'-, where: Sp' represents a straight-chain or branched alkylene having 1 to 20, preferably 1 to 12, C atoms, which is optionally mono- or polysubstituted by F, Cl, Br, I or CN, and in which, in addition, one or more non-adjacent CH groups are, independently of one another, -O-, -S-, -NH-, -NR0 -, -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- may be replaced by -, -CH=CH- or -C≡C-, respectively, in such a way that the O and / or S atoms are not directly linked to one another; X' is -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 represents '-, -C≡C-, -CH=CH-COO-, -OCO-CH=CH- or a single bond, R 0 , R 00 and R 000 each, independently of one another, represents H or alkyl having 1 to 12 C atoms, and Y x and Y x‘ each, independently of one another, represents H, F, Cl or CN, X' is preferably -O-, -S-, -CO-, -COO-, -OCO-, -O-COO-, or -CO-NR 0 -,-NR 0 -CO-, -NR 0 -CO-NR 0 - or a single bond.

[0044] A preferred 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 has the meaning indicated above.

[0045] An especially preferred 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 indicated above.

[0046] Particularly preferred radicals Sp′ are, for example, in each case linear ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, undecylene, dodecylene, octadecylene, perfluoroethylene, perfluoropropylene, perfluorobutylene, perfluoropentylene, perfluorohexylene, perfluoroheptylene, perfluorooctylene, perfluorononylene, perfluorodecylene, perfluoroundecylene, perfluorododecylene, perfluorooctadecylene, ethyleneoxyethylene, methyleneoxybutylene, ethylenethioethylene, ethylene-N-methyliminoethylene, 1-methylalkylene, ethenylene, propenylene and butenylene.

[0047] An especially preferred group X' is --O-- or a single bond. In a preferred embodiment, in formula I and its subformulas, the radical T is preferably [ka] represents where R x represents alkyl having 1 to 6 C atoms, preferably methyl.

[0048] In another preferred embodiment, in formula I and its subformulae, the radical T denotes a straight-chain or branched alkyl having 1 to 12 C atoms, in which one or more CH groups are, independently of one another, -C≡C-, -CH=CH-, [ka] or -O-, in such a way that the O atoms are not directly linked to each other, and one or more H atoms may be replaced by halogen, preferably F.

[0049] In a preferred embodiment, the compound of formula I is selected from the compounds of formulae IA-1a to IA-1f, [ka] where T, Z T , [ka] Z 1 , Z 2 , Sp and G have the meanings given above in formula I and preferably T is H, [ka] or a linear or branched alkyl or alkoxy having 1 to 7 C atoms, or a linear or branched alkenyl having 2 to 7 C atoms, preferably a linear alkyl or alkoxy having 1 to 7 C atoms, Z T represents CH2O, OCH2, CH2CH2 or a single bond, preferably a single bond, Z 1 and Z 2represent, identically or differently, CHO, OCH, CHCH, CF0, OCF, C(O)O, OC(O) or a single bond, preferably a single bond, A 1 and A 2 be the same or different, [ka] represents Y 1 represents, at each occurrence, identically or differently, H, F or Cl, preferably H or F; Sp represents a branched or unbranched 1,ω-alkylene having 1 to 12 C atoms, in which one or more non-adjacent CH2- groups may be replaced by O, G is -OP(O)(OH)2, -PO(OH)2, -COH(PO(OH)2)2 or -PO(OR V )2, preferably -PO(OH)2, and R V represents methyl, ethyl or secondary or tertiary alkyl having 1 to 6 C atoms. Highly preferred are compounds of formula IA-1b and IA-1c, especially IA-1b.

[0050] In another preferred embodiment, the compound of formula I is selected from the compounds of formula IA-2: [ka] The groups and parameters appearing herein have the meanings given in formula I above and are preferably A 1 and A 4 be the same or different, [ka] represents; A 3 -Z 3 teeth, [ka] represents; Z T represents a single bond, -CH2O-, -OCH2- or -CH2CH2-; L 1 and L 2 represent, identically or differently, F, CF3 or Cl, Y 2 has, identically or differently, one of the meanings given for formula I above and preferably represents H, F or Cl, Y 3 and Y 4 may be the same or different, R of formula I C and preferably denotes methyl, ethyl, isopropyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclopentenyl, cyclohexyl, cyclohexenyl, methoxy, trifluoromethyl, trifluoromethoxy or trifluoromethylthio, Z 3 represents CH2 or O, Z 1 , Z 2 represent, independently of one another, a single bond, —C(O)O—, —OC(O)—, —CF2O—, —OCF2—, —CHO—, OCH2— or —CH2CH2—, preferably a single bond, G is OP(O)(OH)2, -PO(OH)2, -COH(PO(OH)2)2 or -PO(OR V )2, R V represents methyl, ethyl or secondary or tertiary alkyl having 1 to 6 C atoms, and r and u are independently 0, 1 or 2, and very preferably u is 0 and r is 0 or 1.

[0051] In formula I and its subformulas: [ka] The base is Preferably, [ka] Represents.

[0052] In accordance with another aspect of the present invention, the layer of molecules comprises one or more chiral non-racemic compounds selected from the compounds of formula I.

[0053] Molecular layers derived from chiral compounds of Formula I enable memristor devices to have significantly reduced stochastic noise and faster switching, reducing read and write error rates and having a positive effect on energy efficiency. In addition, an increase in tunneling current is observed, allowing integration into smaller junction sizes.

[0054] Preferably, the chiral compounds have an enantiomeric excess (ee) of greater than 50%, preferably greater than 80%, 90%, or 95%, more preferably greater than 97%, especially greater than 98%.

[0055] Chirality is achieved by a branched chiral group Sp of the above formula I, which has one or more, preferably one or two, very preferably one asymmetrically substituted carbon atoms (or: asymmetric carbon atom, C*), hereinafter referred to as Sp*), in which the asymmetric carbon atom is preferably linked to a substituent selected from the group of two differently substituted carbon atoms, a hydrogen atom, and a halogen (preferably F, Cl, or Br), alkyl or alkoxy having in each case 1 to 5 carbon atoms, and CN.

[0056] a chiral organic radical Sp*, preferably of the formula [ka] and where: X' has the meaning defined above and preferably represents -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, very preferably -O- or a single bond, Q and Q' are the same or different and are a single bond or an optionally fluorinated alkylene having 1 to 10 carbon atoms, where the CH2 group not linked to X can also be replaced by -O-, -CO-, -O-CO-, -CO-O- or -CH=CH-, preferably an alkylene having 1 to 10 carbon atoms or a single bond, particularly preferably (CH2) n5 - or a single bond, n5 is 1, 2, 3, 4, 5, or 6, Y is optionally fluorinated alkyl having 1 to 15 carbon atoms, where one or two non-adjacent CH groups may also be replaced by -O-, -CO-, -O-CO-, -CO-O- and / or -CH=CH-, and further represents CN or halogen, preferably optionally fluorinated alkyl or alkoxy having 1 to 7 C atoms, -CN or Cl, particularly preferably -CH3, -C2H5, -CF3 or Cl.

[0057] In addition, chirality is achieved by the chiral group T of formula I above, which has one or more, preferably one or two, very preferably one, asymmetrically substituted carbon atoms (or: asymmetric carbon atoms, C*) (hereinafter referred to as R*).

[0058] In R*, the asymmetric carbon atom is preferably linked to two different substituted carbon atoms, a hydrogen atom and a substituent selected from the group of halogen (preferably F, Cl, or Br), alkyl or alkoxy in each case having 1 to 5 carbon atoms, and CN.

[0059] The chiral organic radical is preferably of the formula [ka] where X' has the meaning defined above for formula I and preferably represents -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, very preferably -O- or a single bond, Q represents a single bond or an optionally fluorinated alkylene having 1 to 10 carbon atoms, in which the CH groups not linked to X may also be replaced by -O-, -CO-, -O-CO-, -CO-O- or -CH=CH-, preferably an alkylene having 1 to 5 carbon atoms or a single bond, particularly preferably -CH-, -CHCH- or a single bond, Y is optionally fluorinated alkyl having 1 to 15 carbon atoms, in which one or two non-adjacent CH groups may also be replaced by -O-, -CO-, -O-CO-, -CO-O- and / or -CH=CH-, and furthermore CN or halogen, preferably optionally fluorinated alkyl or alkoxy having 1 to 7 C atoms, -CN or Cl, particularly preferably -CH3, -C2H5, -CF3 or Cl, R Ch represents an alkyl group having 1 to 15 carbon atoms different from Y, in which one or two non-adjacent CH groups may also be replaced by -O-, -CO-, -O-CO-, -CO-O- and / or -CH=CH-, preferably a straight-chain alkyl group having 1 to 10, in particular 1 to 7, carbon atoms, in which the CH group linked to the asymmetric carbon atom may also be replaced by -O-, -O-CO- or -CO-O-.

[0060] Preferably, the first and / or second electrode of each cell is made of a metal, a conductive alloy, a conductive ceramic, a semiconductor, a conductive oxide material, a conductive or semiconductive organic molecule, or a layered conductive two-dimensional material. The first and / or second electrode may comprise a combination of more than one of the above materials, for example in the form of a multilayer system. The materials of the first and second electrodes may be selected to be the same or different.

[0061] Suitable metals include Ag, Al, Au, Co, Cr, Cu, Mo, Nb, Ni, Pt, Ru, W, Pd, Pt, with Al, Cr and Ti being preferred. Suitable conductive ceramic materials include CrN, HfN, MoN, NbN, TiO2, RuO2, VO2, NSTO (niobium doped strontium titanate), TaN and TiN, WN, WCN, VN and ZrN, with TiN being preferred.

[0062] Suitable semiconductor materials include indium tin oxide (ITO), indium gallium oxide (IGO), InGa-α-ZnO (IGZO), aluminum doped zinc oxide (AZO), tin doped zinc oxide (TZO), fluorine doped tin oxide (FTO) and antimony tin oxide.

[0063] Suitable elemental semiconductors include Si, Ge, C (diamond, graphite, graphene, fullerenes), α-Sn, B, Se and Te. Suitable compound semiconductors include III-V semiconductors, particularly GaAs, GaP, InP, InSb, InAs, GaSb, GaN, TaN, TiN, MoN, WN, AlN, InN.AlxGal-xAs and InxGal-xNi, II-VI semiconductors, particularly ZnO, ZnS, ZnSe, ZnTe, CdS, CdTe, Hg(l-x)Cd(x)Te, BeSe, BeTex and HgS; and III-VI semiconductors, particularly GaS, GaSe, GaTe, InS, InSex and InTe, I-III-VI semiconductors, particularly CuInSe2, CuInGaSe2, CuInS2 and CuInGaS2, IV-IV semiconductors, particularly SiC and SiGe, IV-VI semiconductors, particularly SeTe.

[0064] Suitable highly doped semiconductor materials include p+Si, n+Si. One example of a suitable layered conductive two-dimensional material is graphene.

[0065] Suitable semiconducting organic molecules include polythiophenes, tetracenes, pentacenes, phthalocyanines, PTCDA, MePTCDI, quinacridones, acridones, indanthrones, flaranthrones, perinones, AlQ3, and mixed systems, particularly PEDOT:PSS and polyvinylcarbazole / TLNQ composites.

[0066] In a preferred embodiment, the first electrode and the second electrode, identically or differently, comprise a material selected from the group consisting of Ag, Al, Au, Co, Cr, Cu, Mo, Nb, Ni, Pt, Ru, Si, W, CrN, HfN, MoN, NbN, TiN, TaN, WN, WCN, VN, and ZrN.

[0067] More preferably, the first electrode and the second electrode, identically or differently, comprise, preferably consist of, a metal nitride selected from CrN, HfN, MoN, NbN, TiN, TaN, WN, tungsten carbide nitride (WCN), VN and ZrN.

[0068] In particular, the first electrode is made of a metal nitride selected from CrN, HfN, MoN, NbN, TiN, TaN, WN, WCN, VN, and ZrN, and the second electrode is made of TiN. Most particularly, the first and second electrodes are both made of TiN.

[0069] In the following description of exemplary embodiments of the present invention, identical or similar components and elements are represented by identical or similar reference numerals, thus avoiding repeated description of these components or elements in individual cases. The figures only diagrammatically depict the subject matter of the present invention.

[0070] FIG. 1A illustrates a nanoscale nonvolatile solid-state resistance device 100 having a molecular switching layer 103 according to an embodiment of the present invention. The device 100 is a two-terminal memory device in this embodiment. The device 100 includes a first electrode 102, a molecular switching layer 103, and a second electrode 104. The device 100 is a resistive memory device in this embodiment, but may be other types of devices in other embodiments. The molecular switching layer can be selectively set to various resistance values ​​by applying and resetting voltages to the electrodes using appropriate control circuitry. The resistance of the device 100 varies depending on the orientation of the molecular dipoles in the molecular switching layer 103. The device 100 is formed on an outer semiconductor substrate 101. The semiconductor substrate may be a silicon substrate or a III-V or II-VI compound substrate. In one embodiment, the substrate is not made of a semiconductor material, but is made of, for example, plastic.

[0071] Particularly suitable substrates are: - elemental semiconductors, Si, Ge, C (diamond, graphite, graphene, fullerenes), - Sn, B, Se and Te, etc.; - Compound semiconductors, preferably - III-V semiconductors, especially GaAs, GaP, InP, InSb, InAs, GaSb, GaN, TaN, TiN, MoN, WN, AlN, InN, Al x Ga 1-x As and In x Ga 1-x Ni, - II-VI semiconductors, especially ZnO, ZnS, ZnSe, ZnTe, CdS, CdSe, CdTe, Hg (1-x) CD (x) Te, BeSe, BeTe x and HgS; -III-VI semiconductors, especially GaS, GaSe, GaTe, InS, and InSe x and InTe, - I-III-VI semiconductors, in particular CuInSe2, CuInGaSe2, CuInS2 and CuInGaS2, -IV-IV semiconductors, especially SiC and SiGe, -IV-VI semiconductors, especially SeTe; - organic semiconductors, in particular polythiophenes, tetracenes, pentacenes, phthalocyanines, PTCDA, MePTCDI, quinacridones, acridones, indanthrones, flavanthrones, perinones, AlQ3, and mixed systems, in particular PEDOT:PSS and polybylcarbazole / TLNQ complexes; - metals, in particular Ta, Ti, Co, Mo, Pt, Ru, Au, Ag, Cu, Al, W and Mg; Conductive oxides, especially indium tin oxide (ITO), indium gallium oxide (IGO), InGa-α-ZnO (IGZO), aluminum-doped zinc oxide (AZO), tin-doped zinc oxide (TZO), fluorine-doped zinc oxide (FTO), and antimony tin oxide is selected from.

[0072] The use of crystalline silicon as substrate 101 is preferred, with textured silicon wafers (100) being particularly preferred here. Textured silicon wafers (100) are employed as conventional substrates in microelectronics and are available with high quality and a low percentage of surface defects.

[0073] In the switching device according to the invention, the molecules of the molecular layer 103 are attached to the first electrode 102 by means of anchor groups G as defined above.

[0074] A molecular layer is optionally disposed on the first electrode 102, e.g., TiO2, A l2 The first electrode 102 may be bonded to a relatively thin (preferably 0.5-5 nm thick) oxidative intermediate layer 105 such as O3, ZrO2, HfO2, or SiO2, and thus in this embodiment the first electrode comprises a first layer comprising a material as defined in claim 1 and a second oxidative layer to which the molecular layer 103 is bonded (FIG. 1B). Thus, the first electrode 102 and intermediate layer 105 can act as an alternative first electrode 102'.

[0075] The molecular layer of the present invention is a layer of an electrically insulating, non-conductive, or non-semiconductive organic compound. The molecular layer is formed essentially from a precursor of formula I. Preferably, the precursor used to form the molecular layer consists of a compound of formula I.

[0076] The thickness of the molecular layer is preferably 10 nm or less, particularly preferably 5 nm or less, very particularly preferably 3 nm or less. The molecular layer may consist of one, two, three or more molecular layers comprising the compound of formula I.

[0077] The molecular layer employed in accordance with the present invention is preferably a molecular monolayer. In one embodiment, the molecular layer is a self-assembled monolayer (SAM).

[0078] The preparation of self-assembled monolayers is known to those skilled in the art and a review is given, for example, in A. Ulman, Chem. Rev. 1996, 96, 1533-1554. The degree of coverage of the substrate is preferably 90% to 100%, particularly preferably 95% to 100%, very particularly preferably 98% to 100%. Preferably, the second electrode 104 is made of TiN.

[0079] In one embodiment, in the embodiment of FIG. 1A, a first electrode 102 implemented in the form of a conductor track running perpendicular to the drawing plane is arranged on a substrate 101 .

[0080] Similar to the first electrode 102, the second electrode 104 in the form of a conductor track is arranged on the side of the molecular layer 103 facing outwards from the substrate 101. However, the second electrode 104 is rotated by 90° relative to the first electrode 102, resulting in a cross-shaped arrangement. This arrangement is also called a crossbar array; here an angle of 90° is chosen as an example, although arrangements in which the second electrode 104 and the first electrode 102 intersect at an angle other than a right angle are also conceivable. At each intersection between the second electrode 104 and the first electrode 102, a switching device 100 is arranged, formed from a layer system comprising, in this order, the second electrode 104, the molecular layer 103 and the first electrode 102. In one embodiment, a diode is also assigned to each switching device 100.

[0081] The crossbar array allows each switching device 100 to be electrically addressed by applying a voltage between the corresponding first electrode 102 and second electrode 104 .

[0082] The manufacture and structuring of the electrodes is carried out by processes known to those skilled in the art and is explained in more detail below with reference to examples.

[0083] The structures of the electrodes 102, 104 can be produced by structuring methods known to those skilled in the art from microelectronics. For example, lithographic methods can be used to produce the first electrode 102. In this, a metal layer is applied to the substrate 101 by means of vapor deposition. This metal layer is then covered with a photoresist, which is exposed by the structures to be produced. After developing and, if necessary, baking the resist, the unnecessary parts of the metal layer are removed, for example, by wet chemical etching. The remaining resist is then removed, for example, using a solvent.

[0084] A further possibility for the production of the electrodes 102, 104 is vapor deposition with the aid of a shadow mask. In this method, a mask with openings corresponding to the shape of the electrodes 102, 104 to be produced is placed on the part, and subsequently a metal is applied by vapor deposition. The metal vapor is able to precipitate on the part only in the areas not covered by the mask and form the electrodes 102, 104.

[0085] Suitable and preferred processes for the fabrication of switching devices according to the present invention are disclosed in EP 3813132, paragraphs

[0113] to

[0126] . The compounds according to the present invention can be used as described therein.

[0086] A substrate 101 is provided on which a plurality of devices 100 are defined. In this embodiment, the substrate is silicon (p-doped, resistivity <0.001 Ω cm -1 , prime grade). In a preferred embodiment, the silicon substrate consists of a SiO2 layer that acts as an isolation layer and improves derivatization. In other embodiments, other semiconductor materials, such as III-V and II-VI semiconductor compounds, may be used as the substrate. Device 100 may be formed as part of a front-end or back-end process, depending on the implementation. Thus, substrate 101 may include one or more layers of material formed and patterned thereon when the substrate is provided for the process.

[0087] The first electrode is formed on the substrate 101 using any deposition process, such as, for example, chemical vapor deposition (CVD), plasma-enhanced CVD (PECVD), radio-frequency CVD (RFCVD), physical vapor deposition (PVD), atomic layer deposition (ALD), molecular beam deposition (MBD), pulsed laser deposition (PLD), and / or liquid source mist chemical deposition (LSMCD), and / or sputtering, or another deposition or growth process that forms at least the top portion of the first electrode. The bottom electrode should preferably comprise a material with a high voltage threshold for ion migration, and it can be blanketed or structured by photolithography or other advanced lithography processes known to those skilled in the art, such as nanoimprint lithography or dip-pen lithography.

[0088] Optionally, the first electrode is treated with oxygen, argon, or nitrogen plasma or UV / ozone to obtain a hydrophilic oxidized surface with hydroxyl groups. It is clear that this type of oxidized surface serves merely as a surface modification for the purpose of possible derivatization by condensation reactions and does not represent a true insulating or intermediate layer. This oxidized surface has a thickness of about 1 nm, so that a sufficiently large tunneling current is possible through it.

[0089] A molecular layer 103 is formed on the first electrode 102 . The deposition of the molecular layer on the first electrode is carried out either pure or from solution, preferably from solution. Compilation Deposition methods and solvents are known to those skilled in the art, examples being spin coating or dip coating.

[0090] In one embodiment, the anchoring group G of the compounds forming the molecular layer, in particular of the compounds of formula I and their sub-formulas, is OH, [ka] -CH(CH2OH)2, -COOH, and -OC(O)-OR 2where R 2 represents primary, secondary or tertiary alkyl having 1 to 6 C atoms, preferably tert.-butyl; preferably the anchor group G is OH, [ka] and -COO, and wherein the molecular layer is formed in an ALD process as described in WO 2021 / 083934. According to another aspect of the present invention, an ALD process is provided, wherein the first reactant of the ALD process has an associated fluorine atom, and wherein the anchor group G of the compound that forms the molecular layer, particularly compounds of formula I and subformulas thereof, is selected from the group consisting of -OSiR3, -COOSiR3, -CH(CH2OSiR3), [ka] and -OC(O)-OSiR3, is selected from where R, in each occurrence, identically or differently, denotes alkyl having 1 to 6 C atoms, preferably methyl, ethyl or isopropyl, very preferably methyl.

[0091] The molecules of the molecular layer are preferably bonded to the first electrode by chemisorption or covalent bonding, more preferably by covalent bonding, for example by condensation with hydroxyl groups located on the surface of the substrate, by known methods familiar to those skilled in the art. In an alternative embodiment, the molecular layer 103 may also be connected not directly but via a thin oxidative adhesion layer 105 made of a metal different from that of the first electrode (e.g., Al2O3, ZrO2), which is deposited on the first electrode using the deposition techniques mentioned above for the first electrode, preferably CVD.

[0092] Preference is given to grafting a molecular layer directly onto the titanium nitride first electrode 102 with molecules of formula I in which the anchor group G is a phosphonic acid group.

[0093] In a preferred embodiment, the device is annealed after deposition of the monolayer. The annealing is carried out at a temperature above 20° C. and below 300° C., preferably above 50° C. and below 200° C., particularly preferably above 90° C. and below 150° C. The time duration of the annealing is between 1 and 48 hours, preferably between 4 and 24 hours, particularly preferably between 8 and 16 hours.

[0094] In another embodiment of the invention, the monolayer is fabricated from one or more compounds of Formula I, wherein the anchor group G is -SO2OR V , OP(O)(ORV)2, -PO(OR V )2, C(OH)(PO(OR V )2)2, -COOR V or Si(OR V )3, where R V represents alkyl having 1 to 20 carbon atoms, preferably secondary or tertiary alkyl having up to 20 carbon atoms. These compounds are distinguished by particularly high solubility and are well suited to industrial processes such as spin coating. In addition, these compounds can be processed by vapor deposition. These compounds serve as precursors of the corresponding free acids, which can be obtained in situ by heat treatment of the compounds after deposition on the first electrode. The first electrode is then heated to a temperature between 60°C and 300°C, preferably between 100°C and 250°C, in particular between 140°C and 180°C.

[0095] The first electrode 102 is patterned to obtain electrodes extending along a direction (for example, the horizontal direction). In this step, a plurality of first electrodes extending in parallel along the first direction are formed.

[0096] A patterned second electrode is formed on the molecular layer 103 by a lift-off process using a known processing sequence including lift-off photoresist, a patterning step, electrode deposition, and lift-off, or using photoresist. The second electrode 104 may be deposited by, for example, sputtering or atomic layer deposition, preferably by sputtering.

[0097] According to another aspect of the present invention, a plurality of cells are arranged in a three-dimensional array of cells. Thus, the array may extend in two directions in a plane that may be defined by a substrate on which the electronic device is formed, and in a vertical direction perpendicular to this plane. The number of cells arranged in each of the two directions or dimensions of the plane may be extremely high, ranging from at least two to thousands, millions, or even billions of cells. For example, in an arrangement of 1024 cells in the x direction and 1024 cells in the y direction, a single two-dimensional layer of cells contains 1,048,576 cells. Such a two-dimensional array of cells, in which each cell is located at the intersection of two orthogonal electrode lines, is known as a crossbar array.

[0098] The number of levels or layers of cells arranged in a vertical or dimensional manner is typically lower, ranging from 2 to at least 64, preferably at least 1024, or even higher. Preferably, the array contains at least 16 levels of cells, more preferably at least 32 levels of cells, and most preferably at least 64 levels of cells. Such a three-dimensional array of cells is known as a 3D crossbar array or a 3D crosspoint device. [Example]

[0099] example Synthesis Example Example 1: (11-{2-fluoro-4-[4-pentylcyclohexyl]phenoxy}undecyl)phosphonic acid Step 1: Diethyl (11-{2-fluoro-4-[4-pentylcyclohexyl]phenoxy}undecyl)phosphonate [ka] 2-Fluoro-4-(4-pentylcyclohexyl)phenol (5.0 g, 18.9 mmol), diethyl(11-bromoundecyl)phosphonate (9.1 g, 24.6 mmol), potassium carbonate (10.5 g, 75.7 mmol), sodium iodide (0.14 g, 0.95 mmol), and butanone (65 ml) were heated to reflux under nitrogen for 20 hours. The reaction mixture was filtered, and the filtrate was evaporated to dryness to give an orange oil. The oil was purified by column chromatography on silica with ethyl acetate / dichloromethane to give diethyl(11-{2-fluoro-4-[4-pentylcyclohexyl]-phenoxy}undecyl)phosphonate as a colorless oil. 1 H NMR (400 MHz, chloroform-d) δ ppm 0.90 (3 H, t, J=7.0 Hz), 0.96 - 1.09 (2 H, m), 1.15 - 1.51 (31 H, m), 1.52 - 1.66 (2 H, m), 1.67 - 1.92 (8 H, m), 2.39 (1 H, tt, J=12.2, 2.8 Hz), 3.99 (2 H, t, J=6.6 Hz), 4.03 - 4.17 (4 H, m), 6.83 - 6.90 (2 H, m), 6.92 (1 H, d, J=13.4 Hz).

[0100] Step 2: (11-{2-fluoro-4-[(4-pentylcyclohexyl]phenoxy}undecyl)phosphonic acid [ka] Diethyl (11-{2-fluoro-4-[4-pentylcyclohexyl]phenoxy}undecyl)phosphonate (7.1 g, 12.8 mmol) was dissolved in dichloromethane (107 mL) under nitrogen. Bromotrimethylsilane (19.7 g, 128.0 mmol) was added dropwise and stirred overnight. The reaction mixture was evaporated to dryness in vacuo, and the resulting yellow oil was dissolved in methanol (85 mL) and then evaporated again to produce a yellow solid. The solid was redissolved in dichloromethane (67 mL), and then methanol (67 mL) was added. The solution was slowly concentrated in vacuo at 40 °C until crystallization began, at which point distillation was stopped and the flask was transferred to an ice-acetone bath at −5 °C and stirred for 45 minutes. The resulting solid was collected by filtration and washed on the filter with cold methanol (3 x 10 ml) and dried to give (11-{2-fluoro-4-[(4-pentylcyclohexyl]phenoxy}-undecyl)phosphonic acid as a colorless solid. 1 H NMR (400 MHz, THF-d8) δ ppm 0.90 (3 H, t, J=7.0 Hz), 0.98 - 1.14 (2 H, m), 1.18 - 1.52 (26 H, m), 1.53 - 1.67 (4 H, m), 1.70 - 1.80 (2 H, m), 1.81 - 1.92 (4 H, m), 2.40 (1 H, tt, J=12.1, 3.1 Hz), 3.97 (2 H, t, J=6.4 Hz), 6.67 - 7.17 (2 H, m). 19 F NMR (376 MHz, THF-d8) δ ppm -135.71. 31 P NMR (162 MHz, THF-d8) δ ppm 30.62.

[0101] Analogously to Synthesis Example 1, the following compounds were obtained: [Table 1-1] [Table 1-2] [Table 1-3] [Table 1-4] [Table 1-5] [Table 1-6] [Table 1-7] [Table 1-8] [Table 1-9] [Table 1-10] [Table 1-11]

[0102] Device fabrication Preparation of test chips A 45x45mm silicon wafer with a 4nm TiO2 top layer deposited by ALD was treated with ozone for 15 minutes and then immersed in a 1mM solution of phosphonic acid in THF for 72 hours. The chip was dried in a nitrogen stream and then tempered at 120°C for 1 hour. The chip was rinsed with THF and dried in a nitrogen stream.

[0103] Water contact angle measurement The test chip treated with 11-{2-fluoro-4-[(4-pentylcyclohexyl)phenoxy}undecyl)-phosphonic acid has a water contact angle of 100.8°.

[0104] Electrical characterization A silicon wafer treated with 11-{2-fluoro-4-[(4-pentylcyclohexyl)phenoxy}undecyl)-phosphonic acid was bonded to a copper plate cleaned by immersion in 1 M hydrochloric acid using a silver conductive paste. The silver conductive paste was annealed at 80 °C for 10 minutes under a nitrogen flow. The sample was then introduced into a nitrogen glove box and contacted with a capillary of Hg at the bottom and top of the copper contacts. A new Hg droplet was produced for each measurement. The droplet size was measured by a camera system to determine the contact area.

[0105] Four cycles of current-voltage (IV) measurements were taken between -3 and +3 V in 40 mV steps per contact area. For retention measurements, a half cycle of IV measurements from 0 to 3 V and back to 0 V for set operation (low resistance state, LRS) was performed. For reset, IV measurements were taken from 0 to -3 V and back to 0 V (high resistance state, HRS). After a fixed time interval, a short constant voltage measurement at 1 V was taken. The resulting current-voltage curves are shown in Figure 2.

[0106] The measurement results for a reference device without a molecular monolayer are shown in FIG.

Claims

1. A compound represented by formula I, 【Chemistry 1】 During the ceremony T is based on the following: a) Linear or branched alkyl or alkoxy having 1 to 20 carbon atoms each, where one or more CH groups are present in their radicals. 2 The elements are independent of each other: -C≡C-, -CH=CH-, 【Chemistry 2】 -O-, -S-, -CF 2 O-, -OCF 2 -, -CO-O-, -O-CO-, -SiR 0 R 00 -, -NH-,-NR 0 - or - SO 2 -The oxygen atoms may be replaced so as not to be directly bonded to each other, and where one or more hydrogen atoms are halogens, CN, SCN or SF6. 5 It may be replaced by, b) A saturated or partially unsaturated aliphatic ring of 3 to 10 members, where at least one -CH 2 - group is replaced by -O-, -S-, -S(O)-, -SO 2 -, -NR x - or -N(O)R x -, or at least one -CH= group is replaced by -N=, and c) Diamond id radical A group of radicals consisting of the following is selected: Z T , Z 1 , Z 2 , and Z 4 In each occurrence, the single bond, -CF, is identical or different. 2 O-, -OCF 2 -, -CF 2 S-, -SCF 2 -, -CH 2 O-, -OCH 2 -, -C(O)O-, -OC(O)-, -C(O)S-, -SC(O)-, -(CH 2 ) n1 -,-(CF 2 ) n2 -, -CF 2 CH 2 -, -CH 2 CF 2 -, -CH=CH-, -CF=CF-, -CF=CH-, -CH=CF-, -(CH 2 ) n3 O-, -O(CH 2 ) n4 -, -C≡C-, -O-, -S-, -CH=N-, -N=CH-, -N=N-, -N=N(O)-, -N(O)=N-, or -N=CC=N-, where n1, n2, n3, n4 are 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10, either identical or different. Z 3 -O-, -S-, -CH 2 -, -C(O)-, -CF 2 -, -CHF-, -C(R x ) 2 -, -S(O)- or -SO 2 - represents, 【Transformation 3】 In each occurrence, represents an aromatic, heteroaromatic, alicyclic, or heteroaliphatic ring having 4 to 25 ring atoms, identical or different, which may also contain a fused ring and may be monosubstituted by X or R L This may involve single or multiple substitutions, 【Chemistry 4】 represents an aromatic or heteroaromatic ring having 5 to 25 ring atoms, which may also contain a fused ring, and may be monosubstituted by X, or R C This may involve single or multiple substitutions, 【Transformation 5】 teeth, 【Transformation 6】 This represents, X is F, Cl, Br, I, CN, SF 5 , CF 3 OCF 3 , or OCHF 2 Preferably representing Cl or F, most preferably F. R L In each appearance, it represents H, an alkyl having 1 to 6 carbon atoms, an alkenyl having 2 to 6 carbon atoms, or an alkoxy having 1 to 5 carbon atoms, preferably H or an alkyl having 1 to 4 carbon atoms, most preferably H, methyl or ethyl, either identically or differently. R C In each appearance, identically or differently, each represents a linear or branched, optionally fluorinated alkyl, alkoxy, alkylthio, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy, each having 1 to 12 C atoms, or a cycloalkyl or alkylcycloalkyl, each having 3 to 12 C atoms, preferably methyl, ethyl, isopropyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, trifluoromethyl, methoxy, trifluoromethoxy or trifluoromethylthio. Sp represents a spacer group or a single bond. R 0 , R 00 , R x This represents an alkyl group having 1 to 6 carbon atoms in a straight or branched chain. G is -OH, -SH, -SO 2 OH, -OP(O)(OH) 2 , -PO(OH) 2 -C(OH)(PO(OH) 2 ) 2 -COOH, -Si(OR x ) 3 -SiCl 3 -CH=CH 2 ,-POCl 2 ,-COH(PO(OH) 2 ) 2 -CO(NHOH), -CO(NR 0 OH), -Si(NMe 2 ) 3 ;or alkyl groups having 1 to 12 carbon atoms in a straight or branched chain, in which one, two, or three non-geminal hydrogen atoms are replaced by OH groups; or -OC(O)-OR V -OC(O)-Si(OR x ) 3 , PO(OR V ) 2 , SO 2 Ure V Represents a base selected from, R V This represents an alkyl group having 1 to 12 C atoms in a straight chain or branched chain, and r, s, t, and u are 0, 1, or 2, either identical or different. The aforementioned compound.

2. The compounds are, formulas IA-1a to IA-1f 【Transformation 7】 Selected from the group consisting of, In the formula, T, Z T , 【Transformation 8】 Z 1 , Z 2 The compound according to claim 1, wherein Sp and G have the meanings given in claim 1.

3. T is H, 【Chemistry 9】 Alternatively, each represents a linear or branched alkyl or alkoxy having 1 to 7 carbon atoms, or a linear or branched alkenyl having 2 to 7 carbon atoms. Z T CH 2 O, OCH 2 CH 2 CH 2 , or represents a single bond, Z 1 and Z 2 are, identically or differently, CH 2 O, OCH 2 , CH 2 CH 2 , CF 2 O, OCF 2 represent C(O)O, OC(O) or a single bond, A 1 and A 2 They are identical or different. 【Chemistry 10】 It represents, Y 1 In each occurrence, it represents H, F, or Cl, either identically or differently. Sp represents a 1,ω-alkylene having 1 to 12 branched or unbranched carbon atoms, and one or more non-adjacent CH2- groups may be replaced by oxygen. G is -OP(O)(OH) 2 , -PO(OH) 2 , -COH(PO(OH) 2 ) 2 or -PO(OR V ) 2 and R V The compound according to claim 1, wherein is methyl, ethyl, or a secondary or tertiary alkyl having 1 to 6 C atoms.

4. The compound is, formula IA-2: 【Chemistry 11】 A compound according to claim 1, selected from the compounds represented by , wherein the appearing groups and parameters have the meaning given in claim 1.

5. A 1 and A 4 They are identical or different. 【Chemistry 12】 This represents, A 3 -Z 3 teeth, 【Chemistry 13】 This represents, Z T This is a single bond, -CH 2 O-, -OCH 2 - or -CH 2 CH 2 - represents, L 1 and L 2 F, CF are identical or different. 3 Or it represents Cl, Y 2 It has one of the meanings of X given above for formula I, either identically or differently, and preferably represents H, F, or Cl. Y 3 and Y 4 The R of formula I is either identical or different. C It has one of the meanings and preferably represents methyl, ethyl, isopropyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclopentenyl, cyclohexyl, cyclohexenyl, methoxy, trifluoromethyl, trifluoromethoxy, or trifluoromethylthio. Z 3 CH 2 Or it represents O, Z 1 , Z 2 These are independent of each other, with single bonds: -C(O)O-, -OC(O)-, and -CF 2 O-, -OCF 2 -, -CH 2 O-, OCH 2 - or -CH 2 CH 2 - represents, G is -OP(O)(OH) 2 , -PO(OH) 2 ,-COH(PO(OH) 2 ) 2 or -PO(OR V ) 2 This represents, R V represents methyl, ethyl, or a secondary or tertiary alkyl having 1 to 6 carbon atoms, and The compound according to claim 4, wherein r and u are independently 0, 1, or 2.

6. Group 【Chemistry 14】 but, 【Chemistry 15】 The compound according to claim 1, which represents the compound described in claim 1.

7. An electronic switching device (100), in this order, First electrode (102), Molecular layer (103), and Including a second electrode (104), Here, the first and second electrodes are preferably the same or different, and are made of metals selected from Ag, Al, Au, Co, Cr, Cu, Mo, Nb, Ni, Pt, Ru, Si, and W, or CrN, HfN, MoN, NbN, TaNTiN, WN, WCN, VN, ZrN, TiO 2 RuO 2 , VO 2 and a ceramic material selected from niobium-doped strontium titanate, The molecular layer is characterized in that it is essentially formed from one or more compounds represented by formula I as described in any one of claims 1 to 6. The aforementioned electronic switching device (100).

8. An electronic switching device (100) according to claim 7, wherein an interlayer (105) is disposed between a first electrode (102) and a molecular layer (103), the interlayer (105) comprises an oxidizing material, the molecular layer (103) is bonded to the oxidizing material, and the first electrode (102) and the interlayer (105) are operable as a first electrode (102').

9. The oxidizing interlayer is TiO 2 , Al 2 O 3 , ZrO 2 , HfO 2 , or SiO 2 The electronic switching device (100) according to claim 8, including the following:

10. An electronic switching device (100) according to claim 7, wherein a group G of a compound represented by formula I, as defined in claim 1, is bonded to a first electrode (102, 102') by chemiadsorption or covalently.

11. The electron switching device (100) according to claim 8, wherein the molecular layer (103) is a molecular monolayer.

12. An electronic component comprising one or more switching devices (100) as described in claim 8.

13. The electronic component according to claim 12, wherein the component has a number of switching devices (100), and the first electrode (102) and second electrode (104) of the switching devices (100) form a crossbar array.

14. The electronic component according to claim 12, wherein the switching device (100) is configured to change between a state having high electrical resistance and a state having low electrical resistance, and the quotient between the high electrical resistance and the low electrical resistance is between 10 and 100,000.

15. The electronic component according to claim 12, wherein the component is a resistive memory device, a sensor, a field-effect transistor, or a Josephson junction.

16. A method for operating the electronic component according to claim 12, wherein the switching device (100) of the electronic component is switched to a high electrical resistance state by setting the corresponding first electrode (102) to a first potential and the corresponding second electrode (104) to a second potential, the voltage between the two electrodes (102, 104) is greater than a first switching voltage and the first potential is greater than the second potential, and the switching device (100) of the electronic component sets the corresponding first electrode (102) to a third potential, and The method is characterized in that the switching device (100) of the electronic component is switched to a low electrical resistance state by setting the corresponding second electrode (104) to a fourth potential, the voltage between the two electrodes (102, 104) is greater than the second switching voltage, the fourth potential is greater than the third potential, and the state of the switching device is determined by applying a reading voltage between the corresponding electrodes (102, 104) that is less than the first and second switching voltages and by measuring the current flow.

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