Method of manufacturing a molecular layer and electronic assembly comprising the same

Abstract

The present invention relates to a method for manufacturing a molecular layer on a substrate using atomic layer deposition (ALD) technology, for electronic components, in particular for a memory element of the ReRAM type. The invention also relates to a compound for producing said molecular layer and to a memory element comprising said molecular layer.

Description

[0001] The present invention relates to a method for producing a molecular layer on a substrate using atomic layer deposition (ALD) technology for use in electronic components, in particular in memory elements of the ReRAM type, wherein at least one layer of an electronic device and the molecular layer are deposited successively without breaking the vacuum in the deposition chamber. The invention also relates to a compound for producing the molecular layer and a memory element containing the molecular layer.

[0002] Molecular layers, in particular self-assembled monolayers (SAMs), are known to the person skilled in the art (F. Schreiber: "Structure and growth of self-assembling monolayers", Progress in Surface Science, Oxford, GB, Vol. 65, No. 5-8, November 1, 2000, pp. 151-256) and are used in organic electronics, for example, for modifying electrode surfaces.

[0003] In computer technology, storage media that allow for rapid write and read access to stored information are required. Solid-state memory, or semiconductor memory, offers particularly fast and reliable storage because it requires absolutely no moving parts. Currently, dynamic random access memory (DRAM) is predominantly used. DRAM allows for rapid access to stored information, but this information must be regularly updated, meaning that the stored information is lost when the power is removed.

[0004] The prior art also discloses non-volatile semiconductor memories, such as flash memory or magnetoresistive random access memory (MRAM), which retain information even after power is removed. A disadvantage of flash memory is that write access is slow and its 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 in a manner similar to DRAM and has a long lifespan, but this type of memory has not yet established itself due to its difficult production process.

[0005] Another alternative is a memory based on a memristor. 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. Even without a supplied voltage, the state (high or low resistance) is retained, meaning that memristors can be used to implement non-volatile memory.

[0006] Another important application of electrically switchable components is in the field of neuromorphic computing or synaptic computing. In the computer system architecture pursued therein, information is no longer processed sequentially in a classical manner. Instead, the goal is to build circuits in a highly three-dimensional interconnected manner to enable information processing similar to that of the brain. In this type of artificial neuronal network, the biological connections (synapses) between nerve cells are represented by memristive switching elements. In some cases, additional intermediate states (between the digital states "1" and "0") may also be particularly beneficial.

[0007] WO 2012 / 127542 A1 and US 2014 / 008601 A1, for example, disclose organic molecular memories having two electrodes and an active region disposed between them. The active region comprises a molecular layer of a conductive aromatic alkyne whose conductivity can be altered under the influence of an electric field. A similar component based on redox-active bipyridinium compounds is proposed in US 2005 / 0099209 A1.

[0008] Known memories based on changes in conductivity or resistance have the disadvantage that free radical intermediates formed by the molecules flowing through the monolayer by the current are in principle susceptible to degradation processes, which have a negative effect on the service life of the component.

[0009] DE102015000120A1 discloses an electronic component suitable for a memristive device, wherein the component contains a self-assembled monolayer of molecules that can be reoriented in an electric field.

[0010] An important class of substances that can align in an electric field is mesogenic compounds. Mesogenic compounds are known in the art and are compounds containing one or more mesogenic groups. Mesogenic groups are molecular moieties that contribute significantly to the formation of low-molecular-weight substances in liquid crystal (LC) mesophases due to the anisotropy of their attractive and repulsive interactions (C. Tschierske, G. Pelzl, S. Diele, Angew. Chem. 2004, 116, 6340-6368). In practice, the ability of mesogenic compounds with polar substituents to align and reorient in an electric field is exploited in liquid crystal displays (Klasen-Memmer, M., and Hirschmann, H., 2014. Nematic Liquid Crystals for Display Applications. Handbook of Liquid Crystals. 3:11:4:1-25.).

[0011] DE102015000120A1 discloses an electronic component suitable for a memristive device, wherein the component contains a self-assembled monolayer of molecules that can be reoriented in an electric field.

[0012] Mesogenic compounds containing terminal polar anchoring groups are also known in principle from the prior art. JP 2007177051A describes mesogenic compounds with positive dielectric anisotropy proposed for the derivatization of iron oxide nanoparticles; the binding to the particles occurs via phosphate, phosphonate, or carboxylate groups located at the end of the side chains. WO 2013 / 004372A1 and WO 2014 / 169988A1 disclose mesogenic compounds with terminal hydroxyl groups for derivatization of substrates for liquid crystal displays to achieve homeotropic alignment of the liquid crystals. JP 2005 / 002164A discloses the corresponding use of dielectrically neutral and positive mesogenic compounds containing polar anchoring groups.

[0013] The method for producing SAMs described in DE102015000120A1 is dip-coating or is referred to as the method for T-BAG method, wherein slow evaporation contains the solvent of the compound to be applied (referring to people such as EL Hanson, J.Am.Chem.Soc.2003,125,16074-16080). These tedious methods are not very suitable for commercial use. Industrially available method is particularly spin coating, also has spraying, slot die coating and conventional printing method, such as inkjet printing, screen printing and micro-contact embossing. Especially when using the compound that contains free acid group as the formation monolayer of anchoring group, the problem that occurs is that they are only fully soluble in high polarity solvents, such as THF, ethanol or isopropanol. These solvents also compete with the combination of substrate and therefore reduce the quality of monolayer with the compound that forms monolayer.

[0014] It is an object of the present invention to provide an improved method for producing a memory element.

[0015] A further object of the present invention is to provide compounds which are suitable for producing memory elements using methods customary in the memory industry.

[0016] In order to solve this problem, the method defined in the following embodiment 1 is provided:

[0017] Embodiment 1: A method for producing an electronic component (100), the method comprising at least the following steps

[0018] (i) providing a substrate having a surface capable of serving as a first electrode (102) disposed in a deposition chamber,

[0019] (ii) forming an anchoring layer (103) on the surface by successively exposing the substrate to first and second reactants in an atomic layer deposition process that ends with exposing the substrate to the first reactant to form a reactive surface, and

[0020] (iii) forming a molecular layer (104) on the reactive surface using physical vapor deposition of one or more compounds, wherein the one or more compounds are conformationally flexible and have a conformationally flexible molecular dipole moment and reactive anchoring groups G configured to react with the reactive layer.

[0021] In particular, a conductive layer covered by a switchable molecular layer can be formed by the method according to the present invention.

[0022] The method is characterized by producing a molecular layer with high purity, since the molecular layer is deposited as part of the ALD process, thereby avoiding contamination of the substrate surface by volatile organic compounds in the air and by impurities or decomposition products in the solvent.

[0023] The method is further characterized by high efficiency, since no tool change and consequent vacuum break is required between the ALD step and the molecular layer deposition. Furthermore, an annealing step is unnecessary and the robustness of the process is improved.

[0024] The invention further relates to a substrate for an electronic component, in particular for a memristive device, comprising a conductive layer capable of acting as an electrode covered by a layer of switchable molecules, wherein said substrate is obtainable by the method according to the invention.

[0025] According to another aspect of the present invention, an electronic component is provided, comprising: a substrate comprising a bottom layer capable of serving as a first electrode, an anchoring layer formed using atomic layer deposition, a switchable molecular layer formed using physical vapor deposition, and a top electrode in contact with the molecular layer.

[0026] Preferred embodiments are specified in the dependent claims and can be taken from the description.

[0027] As used herein, the term "RRAM" or "resistive memory device" or "memristive device" means a memory device that uses a molecular switching layer whose resistance can be controlled by an applied voltage.

[0028] Coupon as used herein is understood to refer to a smaller segment of a substrate. BRIEF DESCRIPTION OF THE DRAWINGS

[0030] Figure 1A A schematic diagram showing the layer structure of a nonvolatile memory element.

[0031] Figure 1BA schematic diagram showing a resistive switching memory element.

[0032] Figure 2 An exemplary logarithmic plot schematically illustrates measured current (I) values ​​versus applied voltage (V) for one exemplary embodiment of a memory device having a resistive switching memory element.

[0033] Figure 3 Schematic diagram showing an experimental setup for electrical characterization of an electronic switching device according to the invention.

[0034] Figure 4 The current-voltage curve of the electronic switching device manufactured according to the method of the present invention is shown.

[0035] There is provided a method for the in situ deposition of a molecular layer by means of a precursor as defined above and below, preferably selected from the compounds of formula IA, IB or IC as defined below.

[0036] The method begins by providing a substrate, optionally including a bottom electrode, for optional deposition of the bottom electrode, followed by subsequent deposition of an anchoring layer and a molecular layer, also referred to herein as a resistive switching layer. The substrate may include one or more signal lines or contacts with which the bottom electrode forms an electrical connection during its deposition. The substrate may have a pre-treated surface suitable for ALD.

[0037] ALD utilizes chemical adsorption to deposit a saturated monolayer of reactive precursor molecules on the substrate surface. This is achieved by alternately pulsing appropriate reactive precursors (hereinafter also referred to as first and second reactants) into the deposition chamber. Each injection of reactive precursors is separated by an inert gas purge to provide a new atomic layer that is added to the previously deposited layer, thereby forming a uniform layer on the substrate. This cycle is repeated to form a layer of the desired thickness.

[0038] The basic chemical mechanism involved in atomic layer deposition involves two gas-phase reactive chemical species, typically a metal-organic precursor and a co-reactant that acts as an oxygen source or as a reducing agent. The precursor and co-reactant species are delivered sequentially to a heated reaction zone containing a receiving growth surface (i.e., a substrate) so that there are two time-separated half-reaction steps. The time-separated exposures are ensured by purging the reactor with an inert gas between the reactant exposure steps. The first precursor exposure step results in the first ALD half-reaction. In this step, the precursor chemically reacts and binds to the surface without completely decomposing. The precursor also changes the primary surface termination so that the surface is ready to react with the co-reactant. The remaining vapor products are pumped or pushed out of the deposition zone using an inert gas flow. For the second ALD half-reaction, the co-reactant is delivered to the growth surface where it reacts exothermically on the surface. The vapor products are flushed away and the ALD cycle begins again.

[0039] In one embodiment, the method includes forming the bottom electrode using ALD. This operation may involve one or more cycles, each involving the following four steps: introducing one or more precursors into the deposition chamber to form the absorber layer, followed by removal of these precursors, and then introducing a reactant that will react with the absorber layer to form a portion of the electrode layer or the entire electrode layer, followed by removal of the reactant. The choice of precursors and processing conditions depends on the desired composition, morphology, and structure of the various parts of the electrode. The layer formed during each of the above-mentioned ALD cycles may be about 0.25 to 1000 nm. thick. In some embodiments, this thickness may not be enough for the electrode. The cycle can be repeated multiple times to increase the electrode layer to the desired thickness. In some embodiments, the thickness of the electrode is less than 5nm, or more specifically, less than 3nm. The minimum electrode thickness depends on the resistance of the layer. The electrode layer is required to be continuous and have a sufficiently low resistance compared to the low resistance state (LRS) of the switching layer. ALD can deposit a continuous film as low as 1nm thick, which is still reasonably conductive. In some embodiments, electrodes formed of materials that inherently contain oxygen and can release oxygen (such as TiN) are formed as thinner layers to reduce the total amount of oxygen, thereby preventing undesirable oxidation of the switching layer or interface. In some embodiments, the ALD cycle is repeated using different precursors. Therefore, different parts of the same electrode layer may have different compositions. This method can be used to deposit, for example, tertiary nitrides in the form of nanolaminates.

[0040] A molecular layer is formed directly on the reactive layer generated by the ALD process. This reactive layer is formed as an intermediate through the first half reaction of the ALD process.

[0041] Herein, a layer deposited by an ALD process by successively exposing a substrate to first and second reactants, the atomic layer deposition process ending with exposing the substrate to the first reactant to form a reactive surface on the layer, is referred to as an anchor layer.

[0042] In one embodiment, an anchoring layer is deposited onto a substrate that can serve as a bottom electrode.

[0043] In another embodiment, the anchoring layer is deposited onto the bottom electrode on the substrate. Here, the materials of the bottom electrode and the anchoring layer can be the same or different.

[0044] In the method according to the invention, the anchoring layer is deposited by an ALD process by successively exposing the substrate to a first and a second reactant, the atomic layer deposition process ending with the exposure of the substrate to the first reactant to form a reactive surface on the layer. Since the ALD process ends after the first half-reaction of the ALD cycle, the terminal layer carries an adlayer (reactive surface) composed of reactive intermediates, such as metal-alkyls, metal-hydrides, metal-alkoxys, metal-alkylaminos, metal-diketonates, metal-dienes, metal-arenes, metal-cyclopentadienyls or metal halides, and their subsequent decomposition products (depending on the nature of the first reactant).

[0045] The first and second reactants used in the ALD process according to the present invention can be gases, liquids or solids. However, the liquid or solid reactants should be volatile enough to allow introduction as a gas. The vapor pressure should be high enough to achieve efficient mass transfer. Solid and some liquid precursors may also need to be heated and introduced to the substrate through a heating tube. The necessary vapor pressure should be achieved at a temperature below the substrate temperature to avoid condensation of the precursor on the substrate. Due to the self-limiting growth mechanism of ALD, solid precursors with relatively low vapor pressures can be used, but the evaporation rate may change during the process due to changes in their surface area.

[0046] Suitable first and second reactive gases are known to the skilled person and are described in the literature, for example: ALD database [online]. Atomic Limits 2019 [retrieved on August 30, 2019].

[0047] Preferred first reactive gases and suitable second reactive gases are listed in the table below.

[0048]

[0049]

[0050]

[0051] The reactive layer is reacted with one or more compounds suitable for forming a molecular layer and comprising reactive anchoring groups. The reaction is carried out in the gas phase at a temperature of 100° C. to 400° C., the compounds being applied to the activated surface by direct evaporation (pulsed or continuous) or by a carrier gas stream.

[0052] The compound is an organic compound with a flexible conformation and has a conformationally flexible molecular dipole moment and a reactive anchoring group G.

[0053] As used herein, reactive anchoring groups refer to functional groups that are capable of reacting with the reactive surface obtained by the method according to embodiment 1 as above. In particular, reactive anchoring groups are capable of reacting with reactive surfaces comprising intermediate species selected from, but not limited to, the following groups: metal-alkyls, metal-hydrides, metal-alkoxys, metal-alkylaminos, metal-diketonates, metal-dienes, metal-arenes, metal-cyclopentadienyls, or metal halides. The skilled person will appreciate suitable functional groups depending on the nature of the reactive surface. Examples are amines, thiols, alcohols, phosphonic acids, carboxylic acids, and their derivatives.

[0054] The compound used to form the molecular layer is preferably selected from the compounds of formula I

[0055] G-Sp-(D) 0,1 -E(I)

[0056] wherein G is a reactive anchoring group for reacting with the reactive surface of the anchoring layer. Compound (I) may further contain a spacer group (Sp) for connecting the molecule to the anchoring group, an optional intermediate group (D), and a polar group (E), wherein the molecule can assume different conformations and has a conformation-dependent molecular dipole moment due to the polar group.

[0057] Meso groups are cyclic organic groups which are preferably mesogenic and can be polar or nonpolar.

[0058] The spacers (Sp) are conformationally flexible, enabling the molecule to adopt different conformations and meaning that they have a conformation-dependent molecular dipole moment. "Conformationally flexible" means that the spacers (Sp) are chosen in such a way that they can adopt at least two different conformations.

[0059] The polar groups are generally selected so as to provide the molecule with a permanent dipole moment of at least 0.5 Debye. The permanent dipole moment is preferably greater than 2 Debye, particularly preferably greater than 3 Debye.

[0060] A polar group is preferably a group having at least one bond in which the difference in electronegativity between the atoms involved is at least 0.5, wherein the electronegativity values ​​are determined by the Pauling method.

[0061] Preferred are polar groups selected from the following groups: CN, SCN, NO2, (C1-C4)-haloalkyl, preferably CF3; (C1-C4)-haloalkoxy, preferably OCF3; S(C1-C4)-haloalkyl, preferably SCF3; S(O)2-(C1-C4)-haloalkyl, preferably SO2CF3; SF5, OSF5, N(C1-C4-haloalkyl)2, preferably N(CF3)2; N(CN)2 and (C6-C 12)-haloaryl, preferably mono-, di- or trifluorophenyl.

[0062] Preferred reactive anchoring groups are alkyl carbonates, alcohols and silylated alcohols, very preferably alcohols and silylated alcohols.

[0063] In a preferred embodiment of the present invention, the molecular layer is formed from one or more compounds selected from the group consisting of compounds of formula IA, IB or IC:

[0064] R 1A -(A 1 -Z 1 ) r -B 1 -(Z 2 -A 2 ) s -Sp A -G (IA)

[0065] D 1 -Z D -(A 1 -Z 1 ) r -B 1 -(Z 2 -A 2 ) s -Sp-G (IB)

[0066] R 1C -(A 1 -Z 1 ) r -B 1 -Z L -A 2C -(Z 3 -A 3 ) s -Sp C -G(IC)

[0067] in

[0068] R 1A 、R 1C refers to straight-chain or branched alkyl or alkoxy groups each having 1 to 20 C atoms, wherein one or more CH2 groups in these groups can each independently be replaced by -C≡C-, -CH=CH-, -O-, -S-, -CF2O-, -OCF2-, -CO-O-, -O-CO-, -SiR 0 R 00 -、-NH-、-NR 0- or -SO2- is replaced in such a way that the O atoms are not directly connected to each other and one or more H atoms may be replaced by halogen, CN, SCN or SF5, wherein R 1C Alternatively refers to the group D 1 -Z D , Z D With Z 1 、Z 2 and Z 3 One of the meanings of or refers to a spacer group,

[0069] Z 1 、Z 2 、Z 3 represents, identically or differently on each occurrence, a single bond, -CF2O-, -OCF2-, -CF2S-, -SCF2-, -CH2O-, -OCH2-, -C(O)O-, -OC(O)-, -C(O)S-, -SC(O)-, -(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-,

[0070] n1, n2, n3, n4 are identical or different and are 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10,

[0071] Z L Refers to -O-, -S-, -CH2-, -C(O)-, -CF2-, -CHF-, -C(R x )2-、-S(O)-、-SO2-,

[0072] G denotes optionally silylated OH, or straight-chain or branched alkyl having 1 to 12 C atoms, in which one, two or three non-geminal H atoms are replaced by optionally silylated OH; or

[0073] Alkyl carbonates, where alkyl is a linear or branched alkyl radical having 1 to 12 C atoms, preferably a tertiary alkyl radical; or trialkylsilyl carbonates, where alkyl is an alkyl radical having 1 to 6 C atoms, preferably an n-alkyl radical, very preferably a methyl, ethyl or isopropyl radical,

[0074] D 1means a diamondoid radical, preferably derived from lower diamondoids, very preferably selected from 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

[0075]

[0076] A 1 、A 2 、A 3 represents, identically or differently on each occurrence, an aromatic, heteroaromatic, alicyclic or heteroaliphatic ring having 4 to 25 ring atoms, which may also contain fused rings and which may be mono- or polysubstituted by Y,

[0077] A 2C refers to an aromatic or heteroaromatic ring having 5 to 25 ring atoms, which may also contain fused rings and which may be replaced by Y C Single or multiple substitutions,

[0078] Y, identically or differently on each occurrence, represents F, Cl, CN, SCN, SF5 or linear or branched, in each case optionally fluorinated, alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy having 1 to 12 C atoms, preferably F or Cl,

[0079] Y C represents, identically or differently on each occurrence, F, Cl, CN, SCN, SF5 or linear or branched, in each case optionally fluorinated, alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy having 1 to 12 C atoms, or cycloalkyl or alkylcycloalkyl having in each case 3 to 12 C atoms, preferably methyl, ethyl, isopropyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, trifluoromethyl, methoxy or trifluoromethoxy,

[0080]

[0081]

[0082] These groups can be oriented in two directions,

[0083] L 1 To L 5 independently represent F, Cl, Br, I, CN, SF5, CF3 or OCF3, preferably Cl or F, wherein L 3 Alternatively, H can be represented

[0084] Sp A refers to a spacer group or a single bond, preferably a spacer group,

[0085] Sp refers to a spacer group or a single bond,

[0086] Sp C refers to a spacer group or a single bond, preferably a single bond,

[0087] R 0 、R 00 represent, identically or differently, alkyl or alkoxy radicals having 1 to 15 C atoms, where, in addition, one or more H atoms may be replaced by halogen,

[0088] R x refers to a straight-chain or branched alkyl group having 1 to 6 C atoms, and

[0089] r, s are 0, 1 or 2, the same or different at each occurrence.

[0090] In a preferred embodiment, the anchoring group G of the molecular layer-forming compound, in particular of the compound of formula IA, IB or IC and subformulae thereof, is selected from OH, -CH(CH2OH)2, -COOH and -OC(O)-OR 2 , where R 2 It refers to a primary, secondary or tertiary alkyl group having 1 to 6 C atoms, preferably tert-butyl.

[0091] Very preferably, the anchoring group G is selected from OH, -CH(CH2OH)2 and -COOH.

[0092] According to another preferred embodiment of the present invention, a method is provided, wherein the first reactant of the ALD process has a fluorine atom attached thereto, and wherein the anchoring group G of the compound forming the molecular layer, in particular the compound of formula IA, IB or IC and subformulae thereof, is selected from the group consisting of -OSiR3, -COOSiR3, -CH(CH2OSiR3)2, and -OC(O)-OSiR3, where R, identically or differently on each occurrence, represents alkyl having 1 to 6 C atoms, preferably methyl, ethyl or isopropyl, very preferably methyl.

[0093] The term "diamondoids" refers to substituted and unsubstituted caged compounds of the adamantane series, including adamantane, bisamantane, triamantane, tetraamantane, pentamantane, hexamantane, heptamantane, octamantane, and the like, including all isomers and stereoisomers thereof. The compounds have an "adamantane-like" topology, meaning that their carbon atoms are arranged so as to overlap on a fragment of the face-centered cubic diamond lattice. Substituted adamantanes from the first series, having from one to four independently selected alkyl or alkoxy substituents, are preferred.

[0094] Adamantanes include "lower adamants" and "higher adamants" (as such terms are defined herein), as well as mixtures of any combination of lower and higher adamants. The term "lower adamants" refers to adamantane, diamantane, and triamantane, as well as any and / or all unsubstituted and substituted derivatives of adamantane, diamantane, and triamantane. These lower adamantane components do not exhibit any isomers or chirality and are easily synthesized, which distinguishes them from "higher adamants." The term "higher adamantane" 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; as well as mixtures of the foregoing and isomers and stereoisomers of tetramantane, pentamantane, hexamantane, heptamantane, and octamantane. 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 family and can be considered a single cage-like crystalline subunit. Diamantane contains two subunits, triamantane contains three, tetraamantane contains four, and so on. Adamantane, diamantane, and triamantane have only one isomeric form, while tetraamantane has four different isomers (two of which represent a pair of enantiomers), i.e., four different possible ways of arranging the four adamantane subunits. The number of possible isomers increases nonlinearly with each higher member of the adamantane family (pentamantane, hexamantane, heptamantane, octamantane, etc.). Adamantane has been extensively studied and is commercially available. Research has been directed to 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 adamantane and its use in forming large-area SAMs on silver and gold surfaces. In KT Narasimha et al., Nature Nanotechnology 11, March 2016, pp. 267-273, a monolayer of adamantane is described as effectively imparting enhanced field emission properties to metal surfaces due to a significant reduction in the work function of the metal.

[0095] A spacer group in the sense of the present invention is a flexible chain between the dipole moiety and the anchoring group, which brings about a separation between these substructures and, due to its flexibility, simultaneously improves the mobility of the dipole moiety after binding to the substrate.

[0096] The spacer group can be branched or straight chain.Chiral spacer groups are branched, optically active and non-racemic.

[0097] Halogen is F, Cl, Br or I, preferably F or Cl.

[0098] In this context, alkyl is linear or branched and has 1 to 15 C atoms, preferably is linear and has, unless otherwise specified, 1, 2, 3, 4, 5, 6 or 7 C atoms, and is therefore preferably methyl, ethyl, propyl, butyl, pentyl, hexyl or heptyl.

[0099] In this context, alkoxy is linear or branched and contains 1 to 15 C atoms. It is preferably linear and has, unless otherwise specified, 1, 2, 3, 4, 5, 6 or 7 C atoms and is therefore preferably methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy or heptyloxy.

[0100] In this article, alkenyl is preferably an alkenyl with 2 to 15 C atoms, which is straight or branched and contains at least one C-C double bond. It is preferably straight and has 2 to 7 C atoms. Therefore, it is preferably vinyl, prop-1- or -2-alkenyl, but-1-, -2- or -3-alkenyl, penta-1-, -2-, -3- or -4-alkenyl, hex-1-, -2-, -3-, -4- or -5-alkenyl, hept-1-, -2-, -3-, -4-, -5- or -6-alkenyl. If two C atoms of the C-C double bond are substituted, the alkenyl can be in the form of E and / or Z isomers (trans / cis). Generally speaking, each E isomer is preferred. Among alkenyl, prop-2-alkenyl, but-2- or -3-alkenyl and penta-3- or -4-alkenyl are particularly preferred.

[0101] In the present context, alkynyl is understood to mean an alkynyl radical having 2 to 15 C 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.

[0102] In formulae IA, IB and IC, preferred aryl groups are derived from, for example, the parent structures benzene, naphthalene, tetralin, 9,10-dihydrophenanthrene, fluorene, indene and indane.

[0103] In the formulae IA, IB and IC, preferred heteroaryl groups are, for example, five-membered rings 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, six-membered rings such as pyridine, pyridazine, pyrimidine, pyrazine, 1,3,5-triazine, 1,2,4-triazine and 1,2,3-triazine. , or a fused ring, such as indole, isoindole, indolizine, indazole, benzimidazole, benzotriazole, purine, naphthimidazole, benzoxazole, naphthioxazole, benzothiazole, benzofuran, isobenzofuran, dibenzofuran, thieno[2,3b]thiophene, thieno[3,2b]thiophene, dithienothiophene, isobenzothiophene, dibenzothiophene, benzothiadiazolothiophene, 2H-chromene (2H-1-benzopyran), 4H-chromene (4H-1-benzopyran) and coumarin (2H-chromen-2-one), or a combination of these groups.

[0104] In formulae IA, IB and IC, preferred cycloaliphatic 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-methylenedihydroindane.

[0105] In formulae IA, IB and IC, preferred heteroaliphatic groups are tetrahydrofuran, dioxolane, tetrahydrothiophene, pyran, dioxane, dithiane, silinane, piperidine and pyrrolidine.

[0106] A 1 and A 2 , independently of one another and identically or differently at each occurrence, are particularly preferably selected from the following group:

[0107] a) 1,4-phenylene, wherein, in addition, one or two CH groups may be replaced by N, and wherein, in addition, one or more H atoms may be replaced by Y,

[0108] 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 replaced by -O- and / or -S-, and wherein, in addition, one or more H atoms may be replaced by Y, and

[0109] 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]octanediyl, piperidine-1,5-diyl and thiophene-2,5-diyl, where, in addition, one or more H atoms may be replaced by Y,

[0110] wherein Y has the meaning indicated above under formula IA and preferably denotes F, Cl, CN or CF3.

[0111] Preferred spacer groups Sp are selected from the formula Sp'-X', so that the group G-Sp- of formula IA corresponds to the formula G-Sp'-X'- and the group D of formula IB 1 -Sp- corresponds to formula D 1 -Sp'-X', and makes the Z of the IC D In the case of a spacer group, the group Dia-Z of formula IC D - corresponds to the formula Dia-Sp'-X'-,

[0112] in

[0113] Sp' is a straight-chain or branched alkylene radical having 1 to 20, preferably 1 to 12, C atoms, which is optionally mono- or polysubstituted by F, Cl, Br, I or CN, and wherein, in addition, one or more non-adjacent CH2 groups may each be independently of one another replaced by -O-, -S-, -NH-, -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 replaced in such a way that O and / or S atoms are not directly connected to each other,

[0114] 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 a single bond,

[0115] R 0 、R 00

[0116] and R 000 each independently of one another represents H or an alkyl group having 1 to 12 C atoms, and

[0117] Y x and Y x‘ Each independently represents H, F, Cl or CN.

[0118] X' is preferably -O-, -S-, -CO-, -COO-, -OCO-, -O-COO-, -CO-NR 0 -、-NR 0 -CO-、-NR 0 -CO-NR 0 - or single key.

[0119] 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- , wherein 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.

[0120] A particularly preferred group -X'-Sp'- is -(CH2) p1 -、-O-(CH2) p1 -、-(CF2) p1 -、-O(CF2) p1 -、-OCO-(CH2) p1 - and -OC(O)O-(CH2) p1 -, wherein p1 has the meaning indicated above.

[0121] 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, vinylene, propenylene and butenylene.

[0122] Particularly preferred groups X' are -O- or a single bond.

[0123] Particularly preferred subformulae of formula IA are the following subformulae IAa to IAf:

[0124] R 1A -B 1 -Sp A -G IAa

[0125] R 1A -(A 1 -Z 1 )-B 1 -Sp A -G IAb

[0126] R 1A -(A 1 -Z 1 )2-B 1 -Sp A -G IAc

[0127] R 1A -B 1 -(Z 2 -A 2 )-Sp A -G IAd

[0128] R 1A -B 1 -(Z 2 -A 2 )2-Sp A -G IAe

[0129] R 1A -(A 1 -Z 1 )-B 1 -(Z 2 -A 2 -)-Sp A -G IAf

[0130] where R1A 、A 1 、A 2 、B 1 、Z 1 、Z 2 、Sp A and G have the meanings indicated above and preferably

[0131] A 1 and A 2 means

[0132]

[0133] B 1 means

[0134]

[0135] These groups can be oriented in two directions,

[0136] R 1A refers to an alkyl group having 1-15 C atoms, preferably 1-7 C atoms, in particular CH3, C2H5, n-C3H7, n-C4H9, n-C5H 11 、n-C6H 13 or n-C7H 15 ,

[0137] L 1 and L 2 independently represent CF3, Cl or F, wherein the group L 1 and L 2 At least one of them is F,

[0138] L 3 It means F,

[0139] Y 1 and Y 2 independently represent H, Cl or F,

[0140] Z 1 、Z 2 independently of one another represent a single bond, -CF2O-, -OCF2-, -CH2O-, OCH2- or -CH2CH2-,

[0141] Sp A refers to a straight-chain 1,ω-alkylene radical having 1 to 12 C atoms,

[0142] G refers to -OH or -OSiMe3 or OSiEt3.

[0143] Very particularly preferred subformulae of the formula IA are the subformulae IAa, IAb and IAd.

[0144] Examples of preferred compounds of Formulae IAa to IAF are shown below:

[0145]

[0146]

[0147]

[0148]

[0149]

[0150]

[0151]

[0152]

[0153]

[0154]

[0155]

[0156]

[0157]

[0158]

[0159]

[0160]

[0161]

[0162] where R 1 With the above definition R 1A and G has the meaning given above and preferably

[0163] R 1A refers to an alkyl group having 1 to 7 C atoms,

[0164] G refers to -OH or -OSiMe3,

[0165] and

[0166] v refers to an integer of 1-12, preferably 2-7.

[0167] Particularly preferred subformulae of formula IB are subformulae IBa to IBf:

[0168] D 1 -Z D -B 1 -Sp-G IBa

[0169] D 1 -Z D -(A 1 -Z 1 )-B 1 -Sp-G IBb

[0170] D 1 -Z D -(A 1 -Z 1 )2-B 1 -Sp-G IBc

[0171] D 1 -Z D -B 1 -(Z 2 -A 2 )-Sp-G IBd

[0172] D 1 -Z D -B 1 -(Z 2 -A 2 )2-Sp-G IBe

[0173] D 1 -Z D -(A 1 -Z 1 )-B 1 -(Z 2 -A 2 )-Sp-G IBf

[0174] Among them D 1 、A 1 、A 2 、B 1 、Z D 、Z 1 、Z 2 , Sp and G have the meanings indicated above.

[0175] In formula IB and its subformulae, very preferably

[0176] A 1 and A 2 Same or different, refers to

[0177]

[0178] B 1 means

[0179]

[0180] D 1 refers to adamantyl or diamantyl, especially adamantyl,

[0181] L 1 and L 2 independently represent CF3, Cl or F, wherein the group L 1 and L 2 At least one of them is F,

[0182] L 3 It means F,

[0183] Y 1 and Y 2 independently represent H, Cl or F,

[0184] Z D Refers to a single bond, -C≡C-, -C(O)O-, -OC(O)-, -OCH2-, -CH2O-, -CH2CH2-, -CH2CH2CH2- or -CH2CH2CH2CH2-,

[0185] Z 1 、Z 2 independently represent a single bond, -C(O)O-, -OC(O)-, -CF2O-, -OCF2-, -CH2O-, -OCH2-, -CH2CH2-, particularly preferably a single bond,

[0186] Sp denotes straight-chain 1,ω-alkylene having 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12 C atoms,

[0187] G refers to -OH or OSiMe3.

[0188] In a further preferred embodiment, in the compounds of formulae IBa to IBf,

[0189] Sp refers to a linear 1,ω-perfluoroalkylene group having 1 to 12 C atoms,

[0190] Among them D 1 、A 1 、A 2 、B 1 、Z 1 、Z 2 and G have the meanings indicated above.

[0191] Very particularly preferred subformulae of formula IB are subformulae IBa, IBb and IBd, in particular the following compounds:

[0192]

[0193]

[0194]

[0195]

[0196]

[0197]

[0198]

[0199] Among them D 1 、Z D and G have the meanings given above and preferably D 1 refers to adamantyl or diamantyl,

[0200] Z D Refers to -CH2O-, -C≡C- or a single bond,

[0201] G refers to -OH or -OSiMe3,

[0202] and wherein v is an integer from 1 to 12, preferably from 2 to 7.

[0203] In formula IC and its subformulae, very preferably,

[0204] A 1 and A 3 Same or different, refers to

[0205]

[0206] A 2 -Z L means

[0207]

[0208] B 1 means

[0209]

[0210] R 1C is H, straight-chain or branched alkyl, alkenyl, alkynyl, alkoxy, adamantyl or adamantylmethoxy, each having up to 12 C atoms,

[0211] L 1 and L 2Identically or differently, F, CF3 or Cl,

[0212] Y 1 and Y 2 Identically or differently, has one of the meanings given above for Y and preferably refers to H, F or Cl,

[0213] Y 3 and Y 4 Same or different, with the above Y 3 and Y 4 means one of the meanings given and preferably refers to methyl, ethyl, isopropyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclopentenyl, cyclohexyl, cyclohexenyl, methoxy, trifluoromethyl, trifluoromethoxy or trifluoromethylthio

[0214] Z L It means -O-,

[0215] Z 1 、Z 2 independently of one another represent a single bond, -C(O)O-, -OC(O)-, -CF2O-, -OCF2-, -CH2O-, OCH2- or -CH2CH2-, in particular a single bond, and

[0216] G refers to -OH, -OSiMe3 or -OSiEt3.

[0217] Very preferred subformulae of formula IC are subformulae IC-1 to IC-6:

[0218]

[0219]

[0220] in

[0221] R 1C has one of the meanings given above,

[0222] L 1 and L 2 Identically or differently, F, CF3 or Cl,

[0223] Y 3 and Y 4 , identically or differently, has one of the meanings given above and preferably refers to methyl, and

[0224] G refers to -OH or -OSiMe3.

[0225] According to another aspect of the invention, the molecular layer comprises one or more chiral non-racemic compounds selected from compounds of formula IA, IB or IC.

[0226] Molecular layers made of chiral compounds of formula IA, IB, or IC enable memristive devices with significantly reduced random noise and faster switching, thereby reducing read and write error rates, which has a positive effect on energy efficiency. Furthermore, enhanced tunneling currents are observed, allowing integration into smaller junction sizes.

[0227] Preferably, the chiral compound has an enantiomeric excess (ee) higher than 50%, preferably higher than 80%, 90% or 95%, more preferably higher than 97%, especially higher than 98%.

[0228] The chirality is achieved by a branched chiral group Sp of the above formula IA or IB (hereinafter referred to as Sp*) having one or more, preferably one or two, very preferably one asymmetrically substituted carbon atoms (or: asymmetric carbon atom, C*).

[0229] In Sp*, the asymmetric carbon atom is preferably connected to two differently substituted carbon atoms, a hydrogen atom and a substituent selected from halogen (preferably F, Cl or Br), alkyl or alkoxy radicals having in each case 1 to 5 carbon atoms and CN.

[0230] The chiral organic group Sp* preferably has the formula

[0231]

[0232] in

[0233] X′ has the meaning defined above for formulae IA and IB and preferably denotes —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,

[0234] Q and Q', identically or differently, represent a single bond or an 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) n5 - or single key,

[0235] n5 is 1, 2, 3, 4, 5 or 6,

[0236] Y is an optionally fluorinated alkyl radical having 1 to 15 carbon atoms, in which one or two non-adjacent CH2 groups may also be replaced by -O-, -CO-, -O-CO-, -CO-O- and / or -CH=CH-, further CN or halogen, preferably an optionally fluorinated alkyl radical or alkoxy radical having 1 to 7 carbon atoms, -CN or Cl, particularly preferably -CH3, -C2H5, -CF3 or Cl,

[0237] In the formula IB, Z D In embodiments where the chiral non-racemic spacer group is present, group D 1 -Sp* preferably has the formula

[0238]

[0239] The radicals occurring therein have the meanings given above.

[0240] Furthermore, the chiral group R of the above formula IA has one or more, preferably one or two, very preferably one asymmetrically substituted carbon atom (or: asymmetric carbon atom, C*). 1A or the chiral group R of the above formula IC 1C The chirality is achieved, hereinafter referred to as R*.

[0241] In R*, the asymmetric carbon atom is preferably connected to two differently substituted carbon atoms, a hydrogen atom and a substituent selected from halogen (preferably F, Cl or Br), alkyl or alkoxy radicals having in each case 1 to 5 carbon atoms and CN.

[0242] The chiral organic group preferably has the formula

[0243]

[0244] in

[0245] X′ has the meaning defined above for formula I and preferably denotes —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,

[0246] Q is a single bond or an optionally fluorinated alkylene group having 1 to 10 carbon atoms, wherein the CH2 groups 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,

[0247] Y is an optionally fluorinated alkyl radical having 1 to 15 carbon atoms, in which one or two non-adjacent CH2 groups may also be replaced by -O-, -CO-, -O-CO-, -CO-O- and / or -CH=CH-, further CN or halogen, preferably an optionally fluorinated alkyl radical or alkoxy radical having 1 to 7 carbon atoms, -CN or Cl, particularly preferably -CH3, -C2H5, -CF3 or Cl,

[0248] R Ch It refers to an alkyl group having 1 to 15 carbon atoms, different from Y, in which one or two non-adjacent CH2 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 CH2 group connected to the asymmetric carbon atom may be replaced by -O-, -O-CO- or -CO-O-.

[0249] In which the IC's R 1C refers to the group D as defined above 1 -Z D In one embodiment, the group R* has the formula D 1 -Sp*, wherein Sp* refers to a chiral non-racemic spacer group.

[0250] As described for formula IB, the group D in formula IC 1 -Sp* preferably has the formula

[0251]

[0252] wherein Dia, Q, Y and X' have the meanings defined above, and Q', identically or differently, has the meaning given above for Q.

[0253] The synthesis of compounds of the formula IA, IB or IC is described in the literature, for example in P. Kirsch, M. Bremer, Angew. Chem. Int. Ed. 2000, 39, 4216-4235; M. Bremer, P. Kirsch, M. Klasen-Memmer, K. Tarumi, Angew. Chem. Int. Ed. 2013, 52, 8880-8896; P. Kirsch, V. Reiffenrath, M. Bremer, Synlett 1999, 389-396; WO 2016 / 110301 A1 and WO 2018 / 007337 A2, or can be carried out by methods known per se as described in the literature (for example in standard works such as Houben-Weyl, Methoden der organischen Chemie [Methods of Organic Chemistry]). Chemistry], Georg-Thieme-Verlag, Stuttgart), more precisely under reaction conditions known and suitable for the reaction.

[0254] Silylated compounds of formula IA, IB or IC are generated from the corresponding alcohols by silylation with reagents generally used to protect alcohols (see Wuts, Peter GM Greene's protective groups in organic synthesis. - 4th ed. / Peter GM Wuts, The odora W. Greene, John Wiley & Sons, Inc., Hoboken, New Jersey, 2007).

[0255] According to another aspect of the present invention, compounds of formula IA-1, IB-1 and IC-1 are provided.

[0256] R 1A -(A 1 -Z 1 ) r -(B 1 ) b -(Z 2 -A 2 ) s -Sp A -OC(O)-OR 2 (IA-1)

[0257] D 1 -Z D -(A 1 -Z 1 ) r -(B1 ) b -(Z 2 -A 2 ) s -Sp-OC(O)-OR 2 (IB-1)

[0258] R 1C -(A 1 -Z 1 ) r -(B 1 ) b -Z L -A 2C -(Z 3 -A 3 ) s -Sp C -OC(O)-OR 2 (IC-1)

[0259] wherein the radicals and parameters occurring have the meanings specified above for formulae IA, IB and IC, b is 0 or 1, preferably 1, and R 2 is a primary, secondary or tertiary alkyl radical having 1 to 6 carbon atoms, preferably tert-butyl, or a radical SiR3, where R is an alkyl radical having 1 to 6 carbon atoms, preferably n-alkyl, very preferably methyl, ethyl or isopropyl.

[0260] Alkyl carbonates IA-1, IB-1 and IC-1 can be prepared by methods known to the skilled person, for example from the corresponding hydroxy compounds, for example by treatment with dialkyl dicarbonates as described in the article by T. Hara, SR Durell, MC Myers, DH Appella, J. Am. Chem. Soc. 2006, 128, 1995-2004 or according to the article by Z. Guan, X. Chai, S. Yu, Q. Meng, Q. Wu, Chem. Biol. Drug Des. 2010, 76, 496-504, by reaction with alkyl chloroformates, for example tert-butyl chloroformate.

[0261] In formulas IA-1, IB-1 and IC-1, R 2 Trialkylsilyl carbonates referring to SiR3 are preferably prepared by treating the corresponding tert-butyl carbonate with trialkylsilyl iodide as disclosed in I. Galyker, WC Still, Tetrahedron Lett. 1982, 23, 4461-4464.

[0262] Examples of compounds of formula IA-1, IB-1 and IC-1 are as follows:

[0263]

[0264]

[0265]

[0266]

[0267] Compounds of formula IA-1, IB-1 and IC-1 can also be obtained by solution processing according to the method described in WO 2019 / 238649 A1.

[0268] In the method of depositing SAMs from the liquid phase using alkyl carbonate or trialkylsilyl carbonate, it is preferred to use carbonates with a decomposition temperature below 200°C. The carbonate is deposited on a suitable substrate by spin coating, spray coating, slot casting, ink jet or other printing techniques. The deposition parameters (concentration, viscosity, rotation speed profile for spin coating) are adjusted in such a way that an excess of SAM precursor is deposited per unit area. Typical substrates are oxides (SiO2, Al2O3, TiO2, ITO, IZO, AZO, IGZO, HfO2, ZrO2, etc.), nitrides (Si3N4, TaN4, etc.), and the like. x 、TiN x etc.), mixed nitrogen oxides (TiN x O y 、TaN x O y ) or metals (W, Mo, Co, Cr, Al, Cu, Ag, etc.). A thin adhesion layer of a suitable oxide can be generated by common methods such as ALD, CVD, wet chemistry, or oxygen plasma treatment. The initial SAM precursor layer is dried and then subjected to elevated temperatures (typically 70-250°C). Without wishing to be bound by theory, it is speculated that this annealing step causes thermal decomposition of the compound into carbenium / trialkylsilyl groups, carbon dioxide, and the release of free hydroxyl SAM precursors. In the first step, the carbenium / trialkylsilyl groups undergo an addition reaction with non-metallic surfaces or surface-oxidized metal surfaces, activating the substrate surface. The second step involves the replacement of surface-bound tert-butyl / trialkylsilyl groups with hydroxyl groups of SAM molecules, releasing alcohol / trialkylsilanol groups or corresponding ether / siloxane groups. The remaining alkyl / trialkylsilyl groups are incorporated into the monolayer, passivating non-reactive or sterically hindered surface sites. Excess hydroxyl SAM precursors and byproducts are then washed away with a suitable solvent (PGMEA, ethanol, THF, etc.) with the aid of heating, stirring, or sonication. Optionally, the resulting SAM may be subjected to an additional thermal annealing step or repeated deposition-annealing-rinsing cycles to improve the SAM density.

[0269] Preferred are structures having the mesogenic groups exemplified above. Particularly preferred are such compounds having a dipole moment perpendicular to the long molecular axis.

[0270] The method according to the present invention has the advantage of improved surface passivation: unreacted surface hydroxyl groups can act as electron trap states, thereby reducing the overall performance of SAM-based devices. These potential defects are passivated in situ by small molecules, which can improve device performance and reliability.

[0271] Furthermore, this method provides intermediates with enhanced reactivity towards surface oxides: Surfaces such as SiO2 are rarely functionalized with hydroxyl compounds due to the low reactivity of hydroxyl groups towards these surfaces and the unfavorable thermodynamic equilibrium of the overall reaction. In situ activation of surface oxides by conversion to alcohol or alkylsilanol groups enables free optimization of relevant parameters for surface functionalization (device / process functionality, reactivity, surface binding density, temperature profile) and other deposition or printing techniques.

[0272] Materials used in nanoelectronics, in particular, require extremely high purity standards, such as metal ion concentrations in the ppb or even ppt range. Due to their polarity, alcohols have a high affinity for metal ions and are therefore extremely difficult to purify effectively. Carbonates are relatively nonpolar and can be processed in a much wider variety of solvents, significantly facilitating their purification.

[0273] The substrate and the first and second electrodes may comprise metal and / or any other conductive material.

[0274] The anchoring layer consists of a material obtainable by ALD.

[0275] Preferably, the substrate and the electrodes comprise a material selected from the group consisting of:

[0276] Si, Ge, diamond, graphite, graphene, fullerene, α-Sn, B, Se, Te; GaAs, GaP, InP, InSb, InAs, GaSb, CrN, HfN, GaN, TaN, TiN, MoN, NbN, WCN, WN, AlN, InN, VN, ZrN, AlxGa1-xAs and InxGa1-xNi, ZnO, ZnS, ZnSe, ZnTe, CdS, CdSe, CdTe, Hg(1- x )Cd( x )Te, BeSe, BeTe x and HgS; GaS, GaSe, GaTe, InS, InSe x and InTe, CuInSe2, CuInGaSe2, CuInS2 and CuInGaS2, SiC and SiGe, SeTe;

[0277] Polythiophene, tetracene, pentacene, phthalocyanine, PTCDA, MePTCDI, quinacridone, acridone, indanthrone, flaranthrone, perinone, AlQ3, PEDOT:PSS, and polyvinylcarbazole / TLNQ complex;

[0278] Ta, Ti, Co, Cr, Mo, Nb, Ni, Pt, Ru, Au, Ag, Cu, Al, W and Mg;

[0279] Indium tin oxide, indium gallium oxide, InGa-α-ZnO, aluminum-doped zinc oxide, tin-doped zinc oxide, fluorine-doped tin oxide, and antimony tin oxide.

[0280] In a preferred embodiment, the first and second electrodes 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.

[0281] More preferably, the first and second electrodes identically or differently comprise, preferably consist of, a metal nitride selected from the group consisting of CrN, HfN, MoN, NbN, TiN, TaN, WN, tungsten carbide nitride (WCN), VN and ZrN.

[0282] In particular, the first electrode is composed of a metal nitride selected from CrN, HfN, MoN, NbN, TiN, TaN, WN, WCN, VN and ZrN, and the second electrode is composed of TiN.

[0283] Very particularly preferably, both the first and the second electrode consist of TiN.

[0284] Preferably, the anchoring layer comprises a material selected from Ag, Al, Au, Co, Cr, Cu, Mo, Nb, Ni, Pt, Ru, Si, W, CrN, HfN, MoN, NbN, TiN, TaN, WN, WCN, VN and ZrN, Al2O3, HfO2, RuO2, SiO2, TiO2 and ZrO2.

[0285] In some embodiments, the method may further involve forming a third layer using atomic layer deposition in the same or another deposition chamber. The third layer may be capable of acting as a second electrode and formed on a molecular level, for example, directly contacting the second layer. The method may continue by forming a fourth layer on the third layer without breaking the vacuum in the deposition chamber between forming the third and fourth layers. The fourth layer may be capable of acting as a protective layer and preventing oxidation of the third layer. The fourth layer may be formed using any deposition technique, such as atomic layer deposition, physical vapor deposition, and chemical vapor deposition.

[0286] In some embodiments, the deposition chamber used to deposit the third layer is different from the process chamber used to deposit the first layer and the molecular layer. In this case, the molecular layer can be exposed to the ambient environment before forming the third layer, and the molecular layer protects the bottom layer from oxygen in the ambient environment. Thus, the third layer can be deposited by ALD or by any other deposition method, such as physical vapor deposition or chemical vapor deposition.

[0287] A brief description of a non-volatile resistive memory element is provided as background and for a better understanding of the various features associated with the sequential deposition of electrodes and molecular switch layers. The memory element includes a dielectric material that exhibits resistive switching properties. A normally insulating dielectric can be realized as described herein by a molecular layer comprising the above-mentioned compound (I), through which a tunneling current may flow after applying a sufficiently high voltage. Since the molecules forming the molecular layer have a molecular dipole moment, the resistivity of the molecular layer depends on the orientation of the dipole moment, which can be reoriented from a first orientation to a second orientation in an electric field to change the resistivity of the layer. Therefore, the switch layer can be set or reset (resulting in high or low resistance) by applying a specific voltage.

[0288] The basic building block of a memory element is a stack 100 having a capacitor-like structure. A nonvolatile memory element includes two electrodes and a dielectric material located between the two electrodes. Figure 1A A schematic diagram of a nonvolatile memory element 100 is shown, which includes a top electrode 105, also referred to as the second electrode, a bottom electrode 102, also referred to as the first electrode, and a resistive switching layer (molecular layer) 104 provided between the top electrode 105 and the bottom electrode 102, wherein the molecular layer is bonded to an anchoring layer 103. It should be noted that the references to "top" and "bottom" with respect to the electrodes 105 and 102 are used only to distinguish and do not imply any particular spatial orientation of these electrodes. Other labels are often used to represent the two electrodes, such as "first formed" and "second formed" electrodes or simply "first" and "second". The nonvolatile memory element 100 may also include other components, such as embedded resistors, diodes, and other components. The nonvolatile memory element 100 is sometimes referred to as a memory element or memory cell.

[0289] Figure 1BA schematic diagram of a resistive switching memory element 120 fabricated according to the above-described operations is shown. The resistive switching memory element 120 includes a base layer 101, which can function as a signal line, a protective layer, or other types of layers. In some embodiments, the protective layer on the bottom surface serves the same purpose as the capping layer on the top surface. The base layer 101 provides a surface for depositing a bottom electrode 102. The bottom electrode 102 is disposed between the substrate 101 and the anchoring layer 103, and the molecular layer 104 is bonded to the anchoring layer 103. A top electrode 105 is provided on the molecular layer 104 and may be covered by a top layer 110. The top layer 110 may be a signal line, a capping layer, or other types of layers.

[0290] Now refer to Figure 2 The operation of the non-volatile memory element 100 is briefly described, which illustrates a logarithmic plot of the current passing through the non-volatile memory element vs. the voltage applied to the electrodes of the non-volatile memory element according to some embodiments. The non-volatile memory element 100 can be in a low resistance state (LRS) defined by line 202 or a high resistance state (HRS) defined by line 201. These states are each used to represent a different logical state, for example, HRS represents a logical 1 and LRS represents a logical 0, or vice versa. Therefore, each non-volatile memory element with two resistance states can be used to store one data bit. It should be noted that some non-volatile memory elements can have three or even more resistance states, thereby enabling multi-bit storage in the same cell.

[0291] Without wishing to be bound by theory, the HRS and LRS are defined by the orientation of the molecular dipoles of the molecules forming the molecular layer 104, which acts as a resistive switching layer. The nonvolatile memory element can switch back and forth between the LRS and HRS many times, defined by a set period and a reset period. Furthermore, the nonvolatile memory element can maintain its LRS or HRS for a considerable period of time and withstand multiple read cycles.

[0292] The overall operation of the non-volatile memory element 100 can be divided into a read operation, a set operation (i.e., turning the cell "on"), and a reset operation (i.e., turning the cell "off"). During a read operation, the state of the non-volatile memory element 100, or more specifically, the resistance of the molecular layer 104, can be sensed by applying a sense voltage to the electrodes 102 and 105. The sense voltage is sometimes referred to as a "read" voltage and is used in Figure 2 Indicated by V read If the nonvolatile memory element 100 is in the HRS represented by line 201, then the external read / write circuitry connected to electrodes 102 and 105 will sense the resulting "off" current (I offAs described above, such a read operation can be performed multiple times without switching the nonvolatile memory element 100 between HRS and LRS. In the above example, when the read voltage (V read ), the nonvolatile memory element 100 should continue to output the “off” current (I off ).

[0293] Continuing with the above example, when it is desired to switch the nonvolatile memory element 100 to a different logic state (corresponding to LRS), the nonvolatile memory element 100 is switched from its HRS to its LRS. This operation is called a set operation. This can be achieved by applying a set voltage (V set ) is achieved. Apply the setting voltage (V set ) causes the molecular dipoles in the molecular layer 104 to reorient from the first orientation to the second orientation and switches the nonvolatile memory element 100 from its HRS to its LRS as shown by the dashed line 204.

[0294] In the LRS, the resistance characteristic of the nonvolatile memory element 100 is represented by a line 202. In the LRS, when a read voltage (V read ), the external read / write circuit will sense the resulting “on” current (I on ). Such a read operation can still be performed multiple times without switching the nonvolatile storage element 100 between LRS and HRS.

[0295] It may be desirable to switch the nonvolatile storage element 100 again to a different logic state by switching the nonvolatile storage element 100 from its LRS to its HRS. This operation is referred to as a reset operation and should be distinguished from a set operation, during which the nonvolatile storage element 100 is switched from its HRS to its LRS. During a reset operation, a reset voltage (V reset ) to reorient the molecular layer 104 from the second orientation back to the first orientation, to its first state, and switch the non-volatile memory element 100 from its LRS to its HRS as shown by the dotted line 206. The above describes reading the non-volatile memory element 100 in its HRS. In general, the non-volatile memory element 100 can be switched back and forth between its LRS and HRS multiple times. The read operation can be performed once, multiple times, or not at all in each of these states (between switching operations).

[0296] In some embodiments, the voltage (V set ) is between about 100 mV and 10 V, or more specifically, between about 500 mV and 5 V. The length of the voltage pulse (tset ) can be less than about 100ms, or more specifically, less than about 5ms, or even less than about 100ns. The read voltage (V read ) can be written at a voltage (V set ) is between about 0.1 and 0.5. In some embodiments, the read current (I on and I off ) is greater than about 10 -10 A, or more specifically, greater than about 10 -8 A allows fast state detection by a reasonably small sense amplifier. The length of the read voltage pulse (t read ) can be set with the corresponding voltage pulse length (t set ) is comparable to, or possibly greater than, the write voltage pulse (t reset )short.

[0297] Corresponding to the set voltage (V set ) and reset voltage (V reset ) of the set current and reset current ratio (i.e. high I set / I reset The ratio) can be at least about 5, or more specifically, at least about 10, to make the state of the nonvolatile storage element easier to determine. The nonvolatile storage element should be able to cycle between LRS and HRS for at least about 10 3 times, or more specifically, at least about 10 7 times without failure. Under thermal stress up to 85℃ and small electrical stress, such as constant applied read voltage (V read ), data retention time (t ret ) should be at least about 5 years, or specifically, at least about 10 years. Other considerations may include low current leakage.

[0298] In some embodiments, the bottom electrode 102 and / or the top electrode 105 each have a thickness of less than 500 nm, or more specifically, less than 300 nm. These thickness ranges can be achieved in a controllable manner using the ALD techniques described above. Furthermore, in some embodiments, the thickness of the stack including the electrodes 102 and 105 and the molecular layer 104 is less than 300 nm, or more specifically, less than 100 nm. Example

[0299] Example 1

[0300] In an ALD tool (Veeco Savannah), compound 1 was deposited onto the Al2O3 anchor layer on the substrate as follows:

[0301]

[0302] Coupons (10 × 30 mm) cut from silicon wafers (6″ inch, boron doped, double-sided polished, 625 μm thickness, (100) orientation, 0.001-0.005 Ωcm resistivity, prime grade; native silicon oxide removed by treatment with aqueous hydrofluoric acid (1 vol%, 1 min, RT) just before deposition) were placed in the process chamber and applied with 20 cycles of trimethylaluminum and water (pulse length 0.015 s each; substrate temperature 160°C, nitrogen carrier gas), followed by 5 pulses of trimethylaluminum to form a reactive Al-CH3 terminated surface. Compound (1) was then evaporated (source temperature = 170°C, vacuum ≈ 0.1 Torr) onto the reactive surface (substrate temperature = 160°C, at a constant vapor flow of approximately 0.1 Torr) to form a molecular layer.

[0303] Figure 3 The diagram shows an arrangement 300 for measuring the electrical properties of an electronic component manufactured as described in the above embodiments. A silicon coupon is electrically conductive and serves as a first electrode 102 to provide electrical contact for a molecular layer 104. The electrical connection to the measuring instrument is established via a movable copper plate. To this end, the sample is placed on a copper plate 330 and can be moved relative to a second electrode 105 by moving the copper plate 330. The second electrode 105, serving as an electrical contact for the upper surface of the molecular layer, is a mercury drop electrode 105 connected to a measuring instrument 340. The diameter of the mercury drop 105 is typically approximately 150 μm.

[0304] For electrical measurements, measuring instrument 340 was configured as a source-measurement unit. That is, measuring instrument 340 provided an output voltage via voltage source 380 and simultaneously measured the resulting current via current measurement unit 360. For measurement, a voltage was applied and varied between copper plate 330 and mercury droplet 105, while the current through the sample was measured. The voltage was periodically varied between a predetermined maximum value of +V and a predetermined minimum value of -V, having a triangular waveform. Experiments were conducted using a Keithley 2635 source-measurement unit.

[0305] The characterization results of the device of Example 1 are shown in Figure 4 In the current-voltage curve 400, the voltage increases from 0 V to +3 V in the first scan 401, then from +3 V to -3 V in the scan 402, and from -3 V back to +3 V in the third scan. The device exhibits hysteretic switching due to the presence of the resistive switching layer.

[0306] The water contact angle of the substrate containing the molecular layer was 99°, and ellipsometry showed a layer thickness of 1 nm compared to a reference sample fabricated by ALD under identical conditions but without the final molecular layer deposition step. The presence of the fluorine-containing molecular layer was detected by elemental analysis using XPS. Only negligible amounts of fluorine were detected in the reference sample.

[0307] Example 2:

[0308] Compound 2 was deposited onto the tungsten anchor layer on the substrate as follows:

[0309]

[0310] The test piece described in Example 1 was placed in a process chamber and 70 cycles of tungsten hexafluoride and disilane (pulse length 0.015 s each; substrate temperature 150°C, nitrogen carrier gas) were applied to form an activated WF-decorated surface. Then, compound (1) was evaporated (source temperature = 170°C, vacuum approximately 0.1 Torr) onto the activated surface (substrate temperature = 160°C, at a constant vapor flow of approximately 0.1 Torr) to form a molecular layer.

[0311] Using a similar method, an activated surface was prepared for subsequent reaction with a compound of Formula IA, IB, or IC as follows: If not otherwise specified, the base pressure was set to 0.1-1 Torr, and the flow rates of the carrier gas and purge gas were adjusted to 50 sccm and 150 sccm, respectively.

[0312] ZrO2-SAM: substrate temperature 250℃; 1. Zr(NEt2)4; 2. H2O; n cycles of 1. and 2.; followed by a pulse of Zr(NEt2)4;

[0313] HfO2-SAM: substrate temperature 250℃; 1. Hf(NEt2)4; 2. H2O; n cycles of 1. and 2.; followed by a pulse of Hf(NEt2)4;

[0314] Cr-SAM: substrate temperature 200℃; 1.Cr((Me)( t Bu)COCNtBu)2; 2.BH3(NHMe2); n cycles of 1. and 2.; followed by a pulse of Cr((Me)(tBu)COCNtBu)2;

[0315] Co-SAM: substrate temperature 200℃; 1.Co((Me)( t Bu)COCNtBu)2; 2.BH3(NHMe2); n cycles of 1. and 2.; followed by a pulse of Co((Me)(tBu)COCNtBu)2;

[0316] TiN-SAM: substrate temperature 350°C; 1. Ti(NMe2); 2. NH3 (300W ICP-RF plasma); n cycles of 1. and 2.; followed by a pulse of TiCl4;

[0317] TaN-SAM: substrate temperature 200℃; 1.Ta(N t Bu)(NEt2)3; 2.H2; n cycles of 1. and 2.; followed by a pulse of Ta(N t Bu)(NEt2);

[0318] Si-SAM: substrate temperature 350°C; 1. SiCl4; 2. Si2H6; SiCl4; n cycles of 1. and 2.;

[0319] Ru-SAM: substrate temperature 150°C; 1.Ru(CpEt)(CO)2Et; 2.O2; n cycles of 1. and 2.; followed by a pulse of Ru(CpEt)2;

[0320] RuO2-SAM: substrate temperature 150°C; 1.Ru(CpEt)2; 2.O2; n cycles of 1. and 2. pulse length ratio: 1:20; followed by one pulse of Ru(CpEt)2;

[0321] Here n depends on the desired thickness of the layer and is an integer from 1 to 100.

Claims

1. A method for producing an electronic component, the method comprising at least the following steps (i) providing a substrate having a surface capable of serving as a first electrode (102) disposed in a deposition chamber, (ii) forming an anchoring layer (103) on the surface by successively exposing the substrate to first and second reactants in an atomic layer deposition process that ends with exposing the substrate to the first reactant to form a reactive surface, and (iii) forming a molecular layer (104) on the reactive surface using physical vapor deposition of one or more compounds, wherein the one or more compounds are conformationally flexible and have a conformationally flexible molecular dipole moment and reactive anchoring groups G configured to react with the reactive layer, wherein the molecular layer (104) is formed of one or more compounds selected from the group consisting of compounds of formula IA, IB or IC: R 1A -(A 1 -Z 1 ) r -B 1 -(Z 2 -A 2 ) s -Sp A -G(IA) D 1 -Z D -(A 1 -Z 1 ) r -B 1 -(Z 2 -A 2 ) s -Sp-G(IB) R 1C -(A 1 -Z 1 ) r -B 1 -Z L -A 2C -(Z 3 -A 3 ) s -Sp C -G(IC) in R 1A 、R 1C refers to straight-chain or branched alkyl or alkoxy groups each having 1 to 20 C atoms, wherein one or more CH2 groups in these groups can each independently be replaced by -C≡C-, -CH=CH-, -O-, -S-, -CF2O-, -OCF2-, -CO-O-, -O-CO-, -SiR 0 R 00 -、-NH-、-NR 0 - or -SO2- is replaced in such a way that the O atoms are not directly connected to each other and one or more H atoms may be replaced by halogen, CN, SCN or SF5, wherein R 1C Alternatively refers to the group D 1 -Z D , Z D With Z 1 、Z 2 and Z 3 One of the meanings of or refers to a spacer group, Z 1 、Z 2 、Z 3 represents, identically or differently on each occurrence, a single bond, -CF2O-, -OCF2-, -CF2S-, -SCF2-, -CH2O-, -OCH2-, -C(O)O-, -OC(O)-, -C(O)S-, -SC(O)-, -(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, n4 are identical or different and are 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10, Z L Refers to -O-, -S-, -CH2-, -C(O)-, -CF2-, -CHF-, -C(R x )2-, -S(O)- or -SO2-, G is an optionally silylated OH radical, or a linear or branched alkyl radical having 1 to 12 C atoms, wherein one, two or three non-geminal H atoms are replaced by an optionally silylated OH radical; or an alkyl carbonate radical, wherein alkyl is a linear or branched alkyl radical having 1 to 12 C atoms; or a trialkylsilyl carbonate radical, wherein alkyl is an alkyl radical having 1 to 6 C atoms, D 1 refers to the adamantane group, A 1 、A 2 、A 3 represents, identically or differently on each occurrence, an aromatic, heteroaromatic, alicyclic or heteroaliphatic ring having 4 to 25 ring atoms, which may also contain fused rings and which may be mono- or polysubstituted by Y, A 2C refers to an aromatic or heteroaromatic ring having 5 to 25 ring atoms, which may also contain fused rings and which may be replaced by Y C Single or multiple substitutions, Y represents F, Cl, CN, SCN, SF in the same or different manner on each occurrence 5+ , or linear or branched, in each case optionally fluorinated, alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy having 1 to 12 C atoms, Y C represents, identically or differently on each occurrence, F, Cl, CN, SCN, SF5, or linear or branched, in each case optionally fluorinated, alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy having 1 to 12 C atoms, or cycloalkyl or alkylcycloalkyl each having 3 to 12 C atoms, B 1 means These groups can be oriented in two directions, L 1 To L 5 independently represent F, Cl, Br, I, CN, SF5, CF3 or OCF3, wherein L 3 Alternatively, H can be represented Sp A refers to a spacer group or a single bond, Sp refers to a spacer group or a single bond, Sp C refers to a spacer group or a single bond, R 0 、R 00 represent, identically or differently, an alkyl or alkoxy radical having 1 to 15 C atoms, wherein Furthermore, one or more H atoms may be replaced by halogens, R x refers to a straight-chain or branched alkyl group having 1 to 6 C atoms, and r, s are 0, 1 or 2, the same or different at each occurrence.

2. The method according to claim 1, wherein D 1 It is an adamantane group derived from lower adamantane.

3. The method according to claim 1, wherein D 1 Selected from adamantyl, diadamantyl and triadamantyl, where 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.

4. The method according to claim 1, wherein D 1 yes:

5. The method according to claim 1 , wherein Y represents, identically or differently on each occurrence, F or Cl.

6. The method according to claim 1, wherein Y C represents, identically or differently on each occurrence, methyl, ethyl, isopropyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, trifluoromethyl, methoxy or trifluoromethoxy.

7. The method according to claim 1, wherein L 1 To L 5 represents Cl or F independently of each other.

8. A method according to claim 1, wherein prior to steps (ii) and (iii) as recited in claim 1, the first electrode (102) is formed by successively exposing the substrate (101) to first and second reactants in an atomic layer deposition process.

9. The method according to claim 8, wherein the first and second reactants forming the anchor layer (103) and the first and second reactants forming the first electrode (102) are different from each other, respectively.

10. The method according to claim 8, wherein the first and second reactants forming the anchor layer (103) and the first and second reactants forming the first electrode (102) are respectively the same.

11. The method according to any one of claims 1 to 10, wherein forming the anchoring layer (103), forming the reactive surface and forming the molecular layer (104) are performed in a common deposition chamber.

12. The method according to any one of claims 2 to 10, wherein forming the first electrode (102), forming the anchoring layer (103), forming the reactive surface and forming the molecular layer (104) are performed in a common deposition chamber.

13. The method according to any one of claims 2 to 10, wherein the second electrode (105) is formed after the steps of forming the first electrode (102), forming the anchoring layer (103), forming the reactive surface and forming the molecular layer (104).

14. The method of claim 13, wherein the second electrode (105) is formed in a common deposition chamber as claimed in claim 12.

15. The method according to any one of claims 1 to 10, wherein the anchoring group G of the compound forming the molecular layer (104) is selected from OH, -CH(CH2OH)2, -COOH and -OC(O)-OR 2 , where R 2 refers to primary, secondary or tertiary alkyl groups having 1 to 6 C atoms.

16. The method according to any one of claims 1 to 10, wherein the first reactant has a fluorine atom attached thereto, and wherein the anchoring group G of the compound forming the molecular layer (104) is selected from the group consisting of -OSiR3, -COOSiR3, -CH(CH2OSiR3)2, and -OC(O)-OSiR3, where R, identically or differently on each occurrence, represents alkyl having 1 to 6 C atoms.

17. The method according to any one of claims 1 to 10, wherein the substrate (101) comprises a material selected from the group consisting of: Si, Ge, diamond, graphite, graphene, fullerene, α-Sn, B, Se, Te; GaAs, GaP, InP, InSb, InAs, GaSb, CrN, HfN, GaN, TaN, TiN, MoN, NbN, WCN, WN, AlN, InN, VN, ZrN, AlxGa1-xAs and InxGa1-xNi, ZnO, ZnS, ZnSe, ZnTe, CdS, CdSe, CdTe, Hg(1- x )Cd( x )Te, BeSe, BeTe x and HgS; GaS, GaSe, GaTe, InS, InSe x and InTe, CuInSe2, CuInGaSe2, CuInS2 and CuInGaS2, SiC and SiGe, SeTe; Polythiophene, tetracene, pentacene, phthalocyanine, PTCDA, MePTCDI, quinacridone, acridone, indanthrone, flaranthrone, peronone, AlQ3, PEDOT:PSS, and polyvinylcarbazole / TLNQ complex; Ta, Ti, Co, Cr, Mo, Nb, Ni, Pt, Ru, Au, Ag, Cu, Al, W and Mg; Indium tin oxide, indium gallium oxide, InGa-α-ZnO, aluminum-doped zinc oxide, tin-doped zinc oxide, fluorine-doped tin oxide, and antimony tin oxide.

18. A method according to any one of claims 1 to 10, wherein the anchoring layer (103) comprises 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, Al2O3, HfO2, RuO2, SiO2, TiO2 and ZrO2.

19. The method according to any one of claims 2 to 10, wherein the first electrode (102) comprises 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.

20. Layer stack comprising a bottom layer capable of acting as a first electrode (102) and a switchable molecular layer (104), obtainable by a method according to any one of claims 1 to 19.

21. An electronic component comprising a layer stack according to claim 20, comprising a substrate (101), a bottom layer capable of acting as a first electrode (102), an anchoring layer (103) formed using atomic layer deposition; a switchable molecular layer (104) formed using physical vapor deposition, and a second electrode (105) in contact with the molecular layer and optionally, a top layer (110).

22. The electronic component according to claim 21, wherein the electronic component is a resistive memory element.

23. An electronic device comprising an electronic assembly according to claim 21 or 22.

24. A compound selected from the group consisting of compounds of formula IA-1, IB-1 and IC-1 R 1A -(A 1 -Z 1 ) r -(B 1 ) b -(Z 2 -A 2 ) s -Sp A -O-C(O)-O-R 2 (IA-1) D 1 -Z D -(A 1 -Z 1 ) r -(B 1 ) b -(Z 2 -A 2 ) s -Sp-O-C(O)-O-R 2 (IB-1) R 1C -(A 1 -Z 1 ) r -(B 1 ) b -Z L -A 2C -(Z 3 -A 3 ) s -Sp C -O-C(O)-O-R 2 (IC-1) wherein R 1A 、R 1C refers to straight-chain or branched alkyl or alkoxy groups each having 1 to 20 C atoms, wherein one or more CH2 groups in these groups can each independently be replaced by -C≡C-, -CH=CH-, -O-, -S-, -CF2O-, -OCF2-, -CO-O-, -O-CO-, -SiR 0 R 00 -、-NH-、-NR 0 - or -SO2- is replaced in such a way that the O atoms are not directly connected to each other and one or more H atoms may be replaced by halogen, CN, SCN or SF5, wherein R 1C Alternatively refers to the group D 1 -Z D , R 2 is a primary, secondary or tertiary alkyl radical having 1 to 6 C atoms, or a group SiR3, where R is an alkyl radical having 1 to 6 C atoms, Z D With Z 1 、Z 2 and Z 3 One of the meanings of or refers to a spacer group, Z 1 、Z 2 、Z 3 represents, identically or differently on each occurrence, a single bond, -CF2O-, -OCF2-, -CF2S-, -SCF2-, -CH2O-, -OCH2-, -C(O)O-, -OC(O)-, -C(O)S-, -SC(O)-, -(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, n4 are identical or different and are 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10, Z L Refers to -O-, -S-, -CH2-, -C(O)-, -CF2-, -CHF-, -C(R x )2-, -S(O)- or -SO2-, D 1 refers to the adamantane group, A 1 、A 2 、A 3 represents, identically or differently on each occurrence, an aromatic, heteroaromatic, alicyclic or heteroaliphatic ring having 4 to 25 ring atoms, which may also contain fused rings and which may be mono- or polysubstituted by Y, A 2C refers to an aromatic or heteroaromatic ring having 5 to 25 ring atoms, which may also contain fused rings and which may be replaced by Y C Single or multiple substitutions, Y, identically or differently on each occurrence, represents F, Cl, CN, SCN, SF5 or linear or branched, in each case optionally fluorinated, alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy radicals having 1 to 12 C atoms, Y C represents, identically or differently on each occurrence, F, Cl, CN, SCN, SF5 or linear or branched, in each case optionally fluorinated, alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy having 1 to 12 C atoms, or cycloalkyl or alkylcycloalkyl each having 3 to 12 C atoms, B 1 means These groups can be oriented in two directions, L 1 To L 5 independently represent F, Cl, Br, I, CN, SF5, CF3 or OCF3, wherein L 3 Alternatively, H can be represented Sp A refers to a spacer group or a single bond, Sp refers to a spacer group or a single bond, Sp C refers to a spacer group or a single bond, R 0 、R 00 represent, identically or differently, an alkyl or alkoxy radical having 1 to 15 C atoms, wherein Furthermore, one or more H atoms may be replaced by halogens, R x refers to a straight-chain or branched alkyl group having 1 to 6 C atoms, b is 1, and r, s are 0, 1 or 2, the same or different at each occurrence.

25. The compound according to claim 24, wherein D 1 It is an adamantane group derived from lower adamantane.

26. A compound according to claim 24, wherein D 1 Selected from adamantyl, diadamantyl and triadamantyl, where 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.

27. The compound according to claim 24, wherein D 1 yes:

28. A compound according to claim 24, wherein Y represents, identically or differently on each occurrence, F or Cl.

29. The compound according to claim 24, wherein Y C represents, identically or differently on each occurrence, methyl, ethyl, isopropyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, trifluoromethyl, methoxy or trifluoromethoxy.

30. The compound according to claim 24, wherein L 1 To L 5 represents Cl or F independently of each other.

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