TW463183B - Molecular scale electronic devices - Google Patents

Abstract

Molecular scale electronic devices are disclosed. Such devices include at least two conductive contacts, and a conductive path bridging the contacts. The conductive path is able to be written into a perturbed state by a voltage pulse, which can be of high or low conductivity, relative to an initial state. The conductive path comprises organic molecules including at least one electron-withdrawing group. Room temperature negative differential resistance is exhibited by the devices.

Description

4 63 1 A7 B7 V. Description of the Invention (Technical Field) The present invention relates to electronic devices and manufacturing methods thereof, and particularly to such devices and methods using conductive organic materials.

North JSL Tong Jing Chemically assembled electronic devices can be used as an extension of conventional circuits and devices. Such chemically assembled devices include nanoscale or molecular scale t subassemblies. Molecular-scale systems offer the obvious advantages of uniform structure and reduced manufacturing costs. In addition, these molecular components provide advantages such as ease of synthesis and easy-to-use chemical transformation to form a large number of highly variable structures. Summary The present invention is based on the manufacture of molecular-scale electronic devices and combines such devices with useful circuits and components. The molecular scale electronic device includes an active oxidized rimogen center, and the plutonium center as a device has a large negative differential resistance (ND R) including room temperature NDR, large peak-to-valley ratio, and key elements that can exchange conductive states. 3 Molecular scale electronic device via Storing high or low conductivity can be used as a memory device 3 The device can be written 'readable and erasable. In one aspect, the present invention provides an electronic device including at least two contacts, and a single layer of conductive organic material forming a conductive path between the contacts. 3 The conductive path includes at least one electron-drawing group, which may be cyano or isocyanide. Nitro, sulfofluorenyl, y? -Carboxyvinyl 'sulfenyl, cold, wan · dicyanovinyl, haloalkyl'methylfluorenyl, carboxyl, carbonyl, alkoxycarbonyl, and aryloxycarbonyl "1-tetrazolyl '5-gas-1 -tetrazolyl, aminomethylamido or sulfamoyl: preferably cyano'isocyano and nitro" The device has high and low electrical conductivity, And can be between -4- This paper size is applicable to China National Standard (CNS) A4 specification (210 X 297 mm) ------------ "Packing --- (Please read the note on the back first (Item 4 fill out this page) • ^ D,-Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs and printed by the Consumer Cooperatives of the Ministry of Economic Affairs and the Intellectual Property Bureau of employees printed by 463 1 8 A7 _B7 V. Description of the invention (2) Repeat between high and low conductivity Exchange. A low-conductivity state has a current,] at about 100 picoamperes or less than about 1 pico-amp. 200 times, preferably at least about 500 times higher and more preferably at least about 1,000 times higher. A phenyl ring that can be bonded to a conductive path by pulling an electron group = at least one electron donating group can also be present on the conductive path ^ conductive path Includes at least about 70% of the atoms are fluorene or fluorene 2-mixed atoms, and include alternating ethynyl and aryl groups, or at least -phenyl-ethynyl linkages, and at least one phenyl group is substituted with an electron-withdrawing group 3 The conductive path further includes a bonding group that can bond a conductive path to a contact such as a sulfur atom, an oxygen atom, a cyano group, a carboxyl group, a diazonium salt, a self anion, an isocyano group, a phosphine or tellurium, and a selenium atom. ® Road service includes biphenyl or ethoxyl. In another aspect, the invention provides an electric device including two contacts, at least one of which is her contact; and a self-assembling conductive organic sub-layer comprising: Phenyl-ethynyl-substituted phenyl-ethynyl-phenyl linkages are located between the contacts, where substituted phenyls include at least -nitro, and here organic molecules are based on at least the terminal phenyl of the linkage. An isocyano group is bonded to the palladium contact s. In another aspect, the present invention Include a memory circuit including-output, an input, a molecular electronic device (as described above) 'the device here'-the contact bridges the input and output, and the other contact of the device here is at a low potential or ground And a comparator also bridges the input and output, where the comparator is in electrical communication with the reference voltage. A memory array can be manufactured including a plurality of these memory circuits arranged into an addressable array 3 The invention provides a static random access memory unit including at least a first and a second aforementioned molecular electronic device, here the first device-5- This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) Love) —--------- 「-install -------- order -------- * 4 ^ (please fill in note I on the back of Mtl first) 4 6: Ρ Α7 Β7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (one of the contacts is connected to a reference voltage, and the other is connected to a node, and another device here has a contact Of—connected to a low or ground potential, and another connection of the contact to that node, Here the node and further coupled to a low potential or earth potential, also comprising - a gain component. The present invention relates to organic or organometallic molecules whose stored charge is used to self-assemble nanometer-scale molecular devices. Divided devices form electronic programming and erasable memory bits. These bits are compatible with the known threshold levels. The memory position can be configured as a memory unit suitable for a random access memory device. The molecular device of such a memory unit has a long bit holding time (over 10 minutes). As used herein, "co-roller" or "co-probability basis" means an extension system in which 7T electrons are superimposed on the Sp and / or Sp2 atoms. This results in overlapping π-electron densities not only inside each pair of sp and / or sp2-mixed atoms but also between 邛 and / or 叩 2_ mixed atoms. Unless otherwise defined, all technical and scientific terms used herein have definitions generally understood by those skilled in the art as shown in the present invention. Although methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention, suitable methods and materials are described below. All publications, patent applications, patents, and other references mentioned here are also incorporated herein for reference. 3 In case of dispute, this specification includes the definitions. 3 In addition, the materials, methods and examples are for reference only. The purpose of illustration is not limitative. Other features and advantages of the present invention will be clearly explained in the following detailed description and patent application scope. Brief description of the drawing This paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) I —-11 ------- I I-- — I (Please read the precautions on the back first Refill this page) Order _-^ · 6-Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 4 63 1: Α7 ____ Β7 V. Description of the Invention (4) Figure 1 is a schematic diagram of a specific molecular device. : Figure 2 is for the purpose! A close-up view of the dispensing device reveals that pores are formed on the substrate and the contact material. Figure 3 is a close-up close-up view of the molecular device of Figure VII, showing the molecules that make up the conductive path between the contacts. FIG. 4 is a schematic diagram of a memory circuit using a specific molecular device. FIG. 5 is a schematic diagram of an SR · unit using a back-to-back differential resistance arrangement. Figure 6 is a schematic diagram of a basic SRAM circuit using a back-to-back differential resistor device with gain. Figure 7 is a schematic diagram of a basic SRAM circuit using a back-to-back differential resistor device without gain. Figure 8 is the current vs. voltage of a specific molecular device. Figure 9 is the current vs. voltage vs. temperature of a specific molecular device. Mapping. Figure 丨 〇 is a graph of the current versus voltage of a particular molecular device, including the initial state and the write state. Figure Π is the difference between the initial state and the write state described in Figure 10 ^ Figure 12 is the bit holding measurement as a plot of current versus time to obtain the bit holding time constant (r). Figure 13 is a graph of temperature dependence of τ, which generates activation energy ^ Figure 14 is a graph of the current versus voltage of a stored state and initial / erased state of a specific molecular device at 60 degrees κ. Figure 15 is a graph of the storage state and initial / erased state of a specific molecular device at 300 degrees κ vs. electric meal. Figure 16 is a measurement logic diagram verification—memory characteristics of a specific molecular device. -7- This paper is suitable for the country's own standard (CNS) A4 size (½ X 297 g) I ---------- install * ----- order -^ (Please read the notes on the back before filling this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 4 63 1 、 A7 B7 V. Description of the invention (5) Figure 17 shows a specific molecular device at 300 degrees K The current is plotted against the voltage. : Figure 18 is a graph of the current of a specific molecular device at 190 degrees K versus voltage. Figure 19 is a graph of the cyclic voltage of a specific molecular device. Figure 20 is the cycle voltage of a specific molecular device. Figure 3 illustrates in detail. Molecular-scale electronic devices include metal contacts and a single layer of conductive organic material to form a conductive path between the contacts. FIG. 1 shows a specific embodiment of a molecular-scale electronic device i including a substrate 3, an insulating material 5 and a cavity 7 3. Further details of the cavity 7 are shown in FIG. 2 'Including the upper contact material 9 and the lower contact material 1 1 and conductive path pores 13. Further details of the conductive path aperture 13 are shown in FIG. 3, including upper and lower contact materials 9 and 11 and specific conductive path molecules 15 = various aspects of these devices are discussed in US Provisional Patent Application No. 60/1 57, i49, application date of September 30, 1999 and 60 / 154,716, application date of September 20, 1999, each case is described here for reference = conductive organic materials that can form conductive paths between metal contacts Manufactured by a substantially conjugated; r electronic system. The conductive path is typically manufactured with two "ends" 'each end contacting a discrete contact. The length of such a conductive path ranges from about 5 Angstroms to about 75 Angstroms, preferably from about 50 Angstroms to about 75 Egypt, more preferably from about 10 Angstroms to about 50 Angstroms. The π-electron system can be manufactured using a molecule that has multiple sp2_ and / or Sp mixed broken, nitrogen, sulfur, or oxygen atoms B adjacent to each other, or-'two consecutive, or less preferably three consecutive sp3- Hybrid carbon, nitrogen, sulfur, or oxygen are pre-separated. For example, the conductive path can be formed from about 4 to about 40 atoms, and most of them are better or better to the paper size. The national standard (CNS) A4 specification (210 X 297 mm) is applicable --J J ------ ----- Install i 1 tf (please read the note 4 on the back before filling out this page) -3 4 63 1 A7 _____B7 V. Description of the invention (6) At least 70% is sp2- and / or SP hybridization. For example, the conductive path contains such a full-carbon aromatic group such as phenyl, tea-based, glycyl'glucanyl, pentyl, heptenyl, biphenylene, indenocenyl, fluorenyl, fluorenyl, Phenaltenyl, phenanthrene 'anthrylphenyl' indinaphthyl '| cenelocene, pentacenyl, hexocenyl, etc .: double bond-containing groups such as ethylene or U-butadienyl; and reference bond groups such as Ethynyl or 1,3-butadiynyl. The conductive path also contains heteroatom-containing groups such as pyridyl, pyridyl, pyrazolyl, pyrrolyl, imidazolyl, fluorenyl, phenylfluorenyl 11 cetyl, naphthalene " > cephenyl, pxanthrene Group, p-losanyl group, sulfanyl group, isobenzoylfuranyl group, benzophenanthranoyl group, oxanthracene group, phenoxathiinyl group, pyrimidinyl group, indolyl group, iso ... Pentyl, indolyl, purinyl, 4-pyridyl, 4-morpholinyl, phthaloyl, pyridinyl, carbazolyl, acridinyl 'phenanthridyl, pyrrolidyl, imidazolinyl, β-indolinyl The isotropic conductive path includes a combination of the foregoing groups such as biphenyl, ethynyl-bibenzyl-ethynyl, vinyl-phenyl-vinyl, pyridyl-ethoxyl-phenyl ' -Ethyl-phenyl, ethynyl_phenyl-ethynyl, phenyl-ethynyl-phenyl-ethynyl, phenyl_ethynyl-phenyl_ethynyl_phenyl, phenyl-vinyl -Phenyl-ethenyl-benzyl, phenyl_vinyl_biphenyl-vinyl-phenyl, biphenyl-vinyl-biphenyl, phenyl_ethynyl_biphenyl-ethynyl -Phenyl 'and many other possible combinations, can Symmetric or asymmetric, regular or non-regular alternation. These groups can be arranged in a branched or unbranched group to form a conductive path = the conductive path also contains an organometallic group such as chromium-arene group. The conductive path also contains at least ~ and optionally several electron-withdrawing groups. These radicals stabilize the radical anion of organic molecules containing conductive paths. This paper size applies to China National Standard (CNS) A4 specifications (21〇X 297 public love) --- ^. *-I I-(Please read the precautions on the back before filling this page)-Intellectual Property of the Ministry of Economic Affairs Printed by the Bureau ’s Consumer Cooperative Cooperative and printed by the Ministry of Economy ’s Intellectual Property Bureau ’s Consumer Cooperative ’s printed d631 B3 A7 ____B7____ _ V. Description of the invention (7) Etc. Sulfofluorenyl, phenylsulfonyl, trifluoromethylsulfonyl, pentafluorophenylsulfinyl, etc.), /?-Carboxyvinyl, sulfinylsulfinyl (such as third butylsulfinylsulfinyl) , Trisulfinyl sulfenyl, trifluorofluorenylsulfinyl sulfenyl, pentafluorophenylsulfinyl sulfenyl, etc.), / ?, /?-Dicyanovinyl, haloalkyl (such as trifluoromethyl, perfluoro Octyl, ω-hydroperfluorinated dodecyl: yl, etc.), methyl ethyl, 'jiji', Jiji (e.g. ethyl ethyl, pentyl, benzyl, trifluoro ethyl, etc.), pit base -And aryloxy condensed groups (such as ethoxyzyl, phenoxycarbon, etc.) '1-tetrakisyl' 5 -Ga-1-tetrakisyl, aminomethyl (such as dodecylaminomethyl) Fluorenyl Methylamino, etc.), aminosulfonyl (such as trifluoromethylamino, fluorenyl, phenylamino, methyl, ethylamino, etc.). Preferred groups are nitro, gamyl and Isocyano 3 These electron-drawing groups are bonded to or are in electronic communication with the atoms of the conductive path, or are bonded to the atoms conjugated to the conductive path or in electronic communication. 3 For example, the electron-drawing group can be directly bonded. To phenyl 'vinyl, benzyl, huiyl, M51, etc .; or can be bonded to a group such as vinyl or ethylene, which in turn is bonded to phenyl, fluorenyl, onion, 4 Indolyl, ethylenyl, etc. 3 The regiochemistry of such electron-drawing groups affects the electronic properties. For example, the variable regiochemistry of aromatic ring systems has differences in conductive properties between regioisomers. 3 Single or multiple electron-drawing groups Can be bonded to a single group such as phenyl, biphenyl, bis, distant, etc. The selective 'electron donating group' can be bonded to an atom of a conductive path or an atom conjugated to a conductive path, or act with such atoms Electron communication 3 For example, the electron donating group can be directly bonded to a wood group, a carbyl group, a hydrazyl group, an ethylene group, etc. Or it can be bonded to a group such as vinyl or ethynyl, which in turn is bonded to -10- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) --- Γ1 ---- — I-install — — — — — Order -------- line. * Ί 1. (Please read the notes on the back & fill in this page first) Λ 63 1 8; Employees of Intellectual Property Bureau, Ministry of Economic Affairs Printed by the consumer cooperative A7 B7 V. Description of the invention () Phenyl, naphthyl, anthryl 'fluorenyl, vinyl, etc. The chemical properties of the region of this electron donating group affect the electronic characteristics. For example, the amine group of the aromatic ring system is changed. Regiochemistry has differences in conductive properties between regioisomers. Suitable a-donor groups include alkoxy, amine, hydroxy, fluorenyl, and thioether groups. An alkoxy group includes a carbon chain containing one oxygen atom and containing {to 6 carbons, which may contain one or two double or reference bonds, is straight or branched, and may be optionally substituted with one or more i | atoms . Alkoxy—The word includes methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, hexyloxy, heptyloxy and the like. The amine group includes first, second and third amines substituted with an alkyl group. Alkyl includes carbon chains containing 1 to 6 carbon atoms. 'Contains one or more double or para-bonds and is straight or branched and optionally substituted with one or more _ atoms. The term alkyl includes methyl' Ethyl, propyl'isopropyl, butyl, isobutyl, third butyl'cis-2-butenyl, trans_2_butenyl, hexyl, heptyl and the like. Conductive path selectivity includes shielding groups such as methylene (_Ch2-) or ethylene (-CH2-CH2-): oxygen atom: sulfur atom; amine group NR_) group, where R is hydrogen, alkyl or substituted alkyl Group: azo-low methyl (-N = CR-), where R is hydrogen, alkyl or substituted gauge; imino (-C (= NR)-), where R is hydrogen, pit or Substituted alkyl group: azo group (-N = N-); azooxy group (-N20-): alkyl group (-NH-NH-) and its alkyl-substituted derivative; fluorenyl group (-C (= NH ) -NH-); melamine (-N = C = N-): guanidino (-NH-C (NH-) = N-): ureido (-NH-C (= 0)- NH-) or heteroadenyl (-N = C (OH) -NH-); etc. These shielding groups can be directly interposed between sp2-and / or sp mixed atoms or interposed between the aforementioned groups forming the conductive path. 3 The shielding group can also be bonded to or electrically communicate with the conductive path without forming a conductive path itself. Part of the 3 is better These shielding bases are combined with the conductive path -11-This paper size applies to the National Park Standard (CNS) A4 specification mo X 297 mm) • n sei I ϋ 1 i 1_ 1 I im · d \ { (Please read the precautions on the back before filling this page) II6. • Tao. 463183 463183 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 --------- B7 ......... ........................ V. The invention description (9) is limited and will not be improperly restricted. The electrical property of the path = In other respects, the choice of f '.. α δ non-sp and / or sp2_ hybrid shielding base can be used to fine-tune the conductivity of the path. The electron pulling group and / or the electron donating group may be included on either or both sides of the shielding group. In a specific example, an appropriate conductive path includes an organic compound represented by phenylacetylene and, for example, the following general formula 1.

EWG: Here X and X are respectively selected from and are mercapto or other sulfur-containing groups such as thioethyl, isocyano, cyano, carboxyl, diazonium salt, phosphine, halide or hydrogen atom or group VIb Atoms such as tellurium, olefins, and other chalcogens: and here ... are integers from J to X. If nl is zero, the conductive path includes a substituted phenyl ring and a bonding group. If nt is greater than 1, at least one of EWGi 3 EWGi and EWG2 is selectively present in the conductive path. If n is greater than 1, EWG2 may be different for different phenyl rings inside η. ΕΝνΟ, ΚΕλνθ2 can be independently selected, and can be a gas group, an isocyano'nitro group, or a gg group (for example, octylphenyl, phenylsulfonyl, trifluorofluorenylsulfonyl, pentafluorophenylsulfinyl) Fluorenyl, etc.), dot-carboxyethylenyl arylene (such as tert-butylsulfinyl, trisalbenzyl, trifluorosulfinyl, pentylene, etc.) ), / 3, fluorene-dicyanoethenyl'halogenated alkynyl (such as trifluorofluorenyl, all-octyl, QJ-hydroper-I-dodecyl, etc.), formamyl, methyl, and carboxyl ( For example, ethenyl, pentamyl, benzyl, trifluoroethyl, etc.), pit- and aryloxy radicals (eg, ethoxycarboxyl, benzyl, etc.), 1-tetrazolyl ， 5-Chloro-1 -tetrayl and aminomethyl -12- This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm)-^ --- I ----- II * I ------ ^ --- ---- (Please read the notes on the back before filling out this page) 4 63 1 8 3 A7 B7 Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs (Group (such as k-based amino fluorenyl, benzyl methyl silk, etc.), amine Decreasing group (such as trifluoromethylaminosulfonyl, benzylaminosulfonyl, ethylamine, etc.) "> A suitable example of Formula 1 is represented by Structural Formula 2, where EWG is The EWG and EWG2t were explained earlier. '

Any molecule can be substituted, detailed later, additional linkages can be introduced between any styl ring or any terminal styl ring 'including methylene, ethylidene, propylidene and other non-sp or sp2-mixed atoms a Conductive shielding, such as an alkyl group, can be located in a conductive path to interrupt the electronic properties of the molecular device. For example, using such electronic change characteristics, a resonant tracking diode can be manufactured. It is possible to synthesize a conductive path which does not obscure one or more spreading, two-contact points, or more contact points or any combination of these characteristics. As shown in the structural formula 1 above, the radical (that is, X and the binding group allows it) The bonding group attached to the aforementioned contact material 3 may be fluorenyl or other sulfur-containing groups such as thioethyl, isocyano, cyano, carboxyl, diazo tweezers' phosphine, anions or hydrogen ions or group VIb atoms such as Tellurium, selenium, and other chalcogens. It is preferred that not all of the bonding groups be argon atoms. In some cases, it is believed that the X or X2 radical expulsion occurs when a single layer of the conductive path is formed. Then, nitrogen can be released when a single layer of conductive path is formed a. If a conductive path containing self-ion separation is used, plutonium atoms can be excluded when forming a single layer of conductive path a I ----- 111-1-¾ ^-I — I --- Order ------- 1 Ϊ < Please read the note on the back? ^ Before filling out this page) -13- Printed by the Consumer Cooperative of Intellectual Property Bureau, Ministry of Economic Affairs

4 63 U A7 --------- B7 _ V. Description of the invention (11) The binding group can be modified and is most suitable for the lowest unoccupied molecular orbital (: LLJM0) or the conductive path and contact material. Overlapping cofferdams, ionicity, or other non-covalent interactions between fermi layers involve between conductive paths and contacts = in this case, the base such as a hydrogen atom is the conductive path atom closest to the contact. Some specific embodiments may involve conductive paths in the form of a Ungmuir-Bododt film, so these specific embodiments do not need to covalently bond groups on either end of the conductive path to the contact 3 The synthesis of such a conductive path includes the synthesis of a group 3 that shields a binding group, such as a thioethyl group, which is an unprotected thiol group, which is used as a conductive path to bond to the binding site surface. In this example, the removal of the protective group using aqueous sodium hydride in aqueous tetrahydrofuran and rapid subsequent processing can produce a twisted group. Additionally and preferably ammonium hydroxide can be provided in situ for removal of acetamidine. In the preferred embodiment of the right stem, any one or both of these binding groups may be bonded to the conductive path. It is also possible that the conductive path includes more than one such binding group on the conductive path-end. The monolayer is expected to be arranged as a molecular assembly, occupying the contact surface. The assembly contains hundreds of thousands to several molecules to a single molecule limit. The surface area of the contacts covered by this type of assembly is in the order of nanometers, in other words, about 1 to about 200 nanometers in diameter. 3 The preferred assembly covers the surface of the contacts about 1 to 50 nanometers in diameter. The contact surface area is covered by a multi-molecular assembly, typically having a roughly circular or oval shape, but other configurations are also possible, such as square or rectangular and have substantially equal or roughly unequal side lengths. The assembly can be regularly arrayed or not. Regular arrangements exist on the contact surface. The arrangement of the better single-layer assembly is essentially regular, as is the case for typical applications such as random access memory devices. 3 For example, the assembly can be 14-i paper size applicable to China National Standards (CNS) A4 specification hiO χ 297 Public -------- l'l ---------- -install ----- l-order *-If !! line (please read the note f on the back before filling (This page) A7 B7

4 63 1 8 3 V. Description of the invention (12) Female hundreds of nanometers or per several micrometers up to several millimeters per line 3 Preferred assembly The interval between the components should be as small as possible, so that the space on the surface of the contact or substrate is used Increase to the maximum. Contacts This January installation includes at least one contact. At each end of the aforementioned conductive path, contact is made by a covalent bond 'by an ionic bond or by the interaction with the penetrating space of the conductive path. Contacts can be made of any highly conductive material or conductive material with a thin layer (less than about 丨 0 angstroms) of an insulating layer, that is, an oxide layer. 3 Metal contacts can be used, and any metal is suitable for use in electronic devices. Metals such as copper, gold, 'palladium', titanium, silver and the like are preferably of medium smoothness' but may also have any useful surface profile or surface geometry. The contacts need not be of pure metal. For example, contacts can be deposited on highly conductive materials across at least a portion of the surface of a lower conductive material. 3 In the manufacture of such contacts, any suitable conventional method can be used to form metal contacts to facilitate the configuration of electrical contacts. For example, metal can be deposited by thermal evaporation, sputtering, laser assisted deposition or chemical deposition on a substrate such as a silicon wafer (for example). Typical insulating layers such as silicon nitride or silicon oxide are then deposited by methods known in the industry. On metal surface. Then, the insulating layer can be selectively removed at a position where an intermolecular-scale electrical device is desired. The removal of the insulating material can be performed, for example, by photolithography or other known methods. This prepared contact is then conveniently used for the formation of a single layer of the self-assembly, the method of forming a Langmuir Blodget film or the construction of a single layer of a mutually conductive material. 3 Specific examples of these methods are described in detail later. The path is deposited on the contacts in the form of a sorted single layer. 3 Preferred single layer density -15- This paper size applies to China National Standard (CNiS) A4 specification (210 X 297 public love) ----------- --Install ---- J --- order ------- • line.-Ί (Please read the precautions on the back to complete this page) Ministry of Economic Affairs Intellectual Property 扃 Employee Consumer Cooperatives Printed Ministry of Economic Affairs Printed by the Intellectual Property Bureau's Consumer Cooperatives 4 63 1 8 · A7 ------- 5. Description of Invention (13) is quite high. In other words, if there are multiple addresses on the contact for the conductive path molecules, as many addresses as possible will be provided by the & molecule 3 to provide this sequence: The method of layers is to assemble a single layer (SAM) by itself Method 3 These methods provide clearly defined, stable, and reproducible metal contacts for self-assembling single layers of conductive paths, such as verified in Zhou et al. Applied Physics Letter u, (丨 997) 6 丨 丨 6 1J 'and The method described here for reference 3 is another way to provide a conductive circuit 牷 single layer is to form a Langmuir Blodget (L-β) film. Such a film can be transferred to a solid substrate by transferring a single layer of a conductive path floating on the liquid surface. In this kind of film, the film thickness and sub-array can be controlled at the molecular level. Such a film generally requires a conductive path to have a hydrophilic end and a hydrophobic end. For example, a molecule having a hydrophilic group such as a carboxylic acid and a hydrophobic group such as a pyrene 5-C 1 5 group can be synthesized. After the SAM or L-B film is deposited, a layer of contact material is deposited on top of the 5αμ. The method of Zhou et al. Is designed to ensure that the deposition of metal atoms accumulates on the SAM surface and does not penetrate into the organic layer. The material forming the contact layer on top of the SAM may be the same as or different from the SAM deposition material. The contacts may have any convenient shape. For some applications, metal coated wafers can be used. The metal contacts may be surfaces that are substantially parallel to each other. The type of the conductive path represented by the general formula 1 can be synthesized according to the general synthesis procedure described below. Secondly, it can be used as a starting material by replacing the electron with a radical or a selective extra electron donating group. For example, the starting material is a molecule such as p-bromoiodobenzyl or 2-'W-5-B-nitrobenzene. Such materials can be single-coupled to triaryl- or trimethyl-silylacetylene using, for example, a sonagasilura coupling procedure. . This reaction product-16- This paper size is applicable to China National Standard (Cns) A4 specification (210 κ 297 mm); *: ------ installation -------- order ---- ----- line f ί (please read the note on the back to fill out this page) 4β3 1 83 Α7 ---------- Β7__ ---------- V. Description of the invention (14) The same coupling agent is then used to couple to the electron-donor or electron-donating substituted or unsubstituted benzylacetylene, but the reaction temperature is higher. Terminal silyl protection can be removed using a typical chemical such as potassium carbonate. The product reacts with an aryl group including a capped or unmasked bonding group = > This type of aryl group also includes a psionic group and / or an electron donating group. For example, the aryl group may be sulfanylthioethyl, such as p-iodothiosulfanylbenzene. Conductive pathways including biphenyls can be constructed in a similar manner and formed via dibasic substitution, such as 4,4 ' -dibrominated or unsubstituted bibenzyl. For example, 2,2, -dinitrate, or 2,2-monobenzyl can be used as a starting material. This kind of material puppet s is located at the 4-and 4 '-positions of the biphenyl ring. The three-block stilbene group and the d-terminal end block can be shown and coupled to the haloaryl group by the general method disclosed here. The base further comprises a covered or uncovered bonding base. This synthetic strategy can be applied to a wide variety of aryl groups including heteroaromatic structures. For example, an electron group can be substituted for p-pyridyl. The product can be used in the coupling procedure 3 device obtained through the reaction of p-nitro-ill-U-pyridine using a copper reactant as the starting material 3 to obtain the product. Properties The molecular devices described herein have useful electronic properties. For example, with negative differential resistance, this property can be observed up to a temperature of at least 300 ° K. Its current has a nonlinear behavior with respect to the voltage ι (ν) curve. The molecular devices described herein can store high or low electrical conductivity, so they can be used as static or dynamic random access memory. The molecular device described here has a memory effect = an electronic device can be used as a memory device by storing a high or low conductivity state. The initial state is written as disturbing dynamics when an applied voltage pulse is applied. The bit that continues to become a storage bit is not changed by a continuous read pulse, but is also a voltage pulse. With pull electronics based on its near -17- This paper size applies to China National Standard (CNS) A4 specifications < 210 X 297 mm) i — 4 ----------- ί · (Please read first Note on the back fill in this page) Order: Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs Printed by the Employee Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 4 6 3 1 b 3 A7 B7

1 A V. Description of the invention () The compound whose terminal is bonded to the conductive path changes its conductive state. Other substituents may be provided in or near the conductive path, including the electron-donating group, and the initial state may be a highly conductive state or a low conductive state. For example, a molecular device including a conductive path having an electron-drawing group such as a nitro group and an electron-donating group such as an acetamino group or an amine group has an initial state, which is a low-conductivity state. The applied voltage pulse converts this initial state into a highly conductive state, which continues to be highly conductive and is not affected by subsequent voltage pulses of the same polarity, which can be used to read the device state. As another example, a molecular device can be prepared that includes a conductive path with an electron-withdrawing group such as a nitro group but no electron-donating group. Although it is not intended to be limited by any specific operating theory, this device is quite difficult to reduce the result when a low potential is applied to form the initial state of the project. It is a high-conductivity state. 3 plus a standard voltage pulse converts this initial state to a low-conductivity state for a period For a long time. For devices with a current density of 50 amps / cm2, the low-conductivity state has a peak current of about 50 picoamps to less than about 1 picoamp. For the same type of device, the highly conductive state has a peak current from about 1 nanoamp to about 100 nanoamps. Such devices have an on-off ratio of about 200 to about 1,000. This number is related to temperature and degree. At 260 degrees K can be as high as about 1000 = electronic devices using molecular-scale devices. Molecular devices can be combined with electronic devices such as the memory circuits and SRAM circuits described herein. A memory circuit using a programmable molecular scale device is shown in Figure 4. The figure shows that the memory circuit 21 includes an input 23, an output 25, and a ground 27. The memory element 29 is a molecular-scale electronic device described herein with leads 3 I and 33 connected to contacts 35 and 37, respectively. The switches 3 9, 4, 1, 43 and 44 can be field effect, for example. -18- This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 cm). --- 7 --------- -Install -------- order --------- line- f (please read the notes on the back-F first to fill in this page) 4 6 3 ϊ-A7 ______ ____B7__ 5. Description of the invention (16) The transistor is controlled by the address decoding circuit and is shown as a loop for simplicity. The amplifiers 45 and 47 are selective depending on the resistance of the ta το member 29. If it is private, you need to zoom in. Comparator 49 is also shown with 5] = In order to write data to the memory, switches 39 and 4 丨 are turned off, so the memory element 29 is connected via the amplifier 45 to the input data. Then turn on the switch. Read the data from the memory, the output switch 43 is closed and the memory element 29 is connected, and the king is more than 49. The "determined" storage state is lower or higher than the reference voltage] 3 According to the result, the output of the comparator 49 is Logic "0" or logic "1" In order to restore the I memory state, switches 41 and 44 are closed. 3 According to methods and architecture known to those in the industry, this circuit can be used for memory arrays. For example, inputs and outputs can be separated and connected to the surface of the wafer to define a grid system. In this way, the addresses of each memory circuit are unique. Molecular-scale devices can also be included in the static random access memory (SRAM) described herein. Figure 5 shows a sram circuit made from a molecular scale device. The SRAM cell 60 includes negative differential resistance devices 61 and 63, each of which is a molecular scale device described herein. RTDs can have the same or different compositions. The two NDR devices are connected in a back-to-back relationship between the positive supply voltage Vref and the ground potential. This produces a circuit with bistable operation. The individual ι_ν characteristics of the two NDR devices are plotted in Fig. 5, where the dashed line is NDR1 'and the solid line ending at (vrst., 〇) is NDR2. As shown in Figure 5, the two devices connected in this way have two stable operating points, that is, two points where the two curves cross, one above the NDR region and one below the NDR region. If there is excessive leakage current at the node SN, 1% ㈤, one of the curves will shift upward, as shown in the figure. 5 It can be exchanged from one stable point to another stable point by supplying a negative or positive current to -19-This paper size applies Chinese National Standard (CNS) A4 Specifications < 210 x 2 mm)-^ ---- ----- II * II (Please read the notes on the back I " fill out this page first) Order-line. Employees of Intellectual Property Bureau, Ministry of Economic Affairs Printed by Consumer Cooperatives 46ό S 3 Α7 '^^ ------- B7___ V. Description of the invention (17) The point SN is generated. If the current taken by the node SN is high enough, the circuit will be changed from VSN high parent to VSN & where VSN is higher than VSN &. Conversely, if the current applied to the point SN is sufficiently high, the circuit will be switched from VSN & to VSN high. The circuit of FIG. 6 shows a specific embodiment of the basic sram unit, in which the switching power < is supplied by the UFET 70 " Thus, the voltage of the node sn is set, the voltage of the node SN drives the gate 3 of the read FET π, and the read FET 76 has another FET 78 as its load. Depending on the voltage of the node SN, the read FET may be turned on or disconnect. The voltage at v is high when it is on and the voltage at V * is low when it is off = Figure 7% shows the simpler $ r a iVI unit, where the readout circuit of Figure 6 is replaced by a simple capacitor. The present invention will be further illustrated by the following examples, but the scope of the present invention is not limited to the scope of the patent application. Examples The following examples illustrate certain specific embodiments of molecular devices and some of their advantages and properties. Initially, some general procedures are explained in the following special cases. Example 1: General conditions Unless otherwise stated, all reactions were performed under a nitrogen atmosphere. Lithium alkyl was obtained from FMC Corporation (Chicago, Illinois). Pyridine, methyl iodide, triethylamine and N, N-dimethylformamide (DMF) were distilled onto calcium hydride and stored on a 4 angstrom molecular sieve. Methylbenzyl and benzene were distilled onto calcium hydride. Digas methane and hexane are distilled: diethyl ether and tetrahydrofuran (THF) are distilled from sodium benzophenone ketal and 3 triethylamine and N, N-diisopropylethylamine are distilled on calcium hydride. Full -20- This paper uses the Chinese standard (CNS) A4 specification (21〇X 297). ---; ------------ Install i 1 (please read the back first) Please pay attention to this page before filling in this page}-| °. Printed by the Employees 'Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs and printed by the Consumers ’Cooperatives of the Ministry of Economic Affairs and printed by the Consumers' Cooperatives of the Ministry of Economic Affairs A7 B7 Dry on 3 angstrom molecular sieve, iH NMR spectrum is 300, 400 or 500 megahertz recorded on Booker (8! ^] ^ 〇 八 1 ^ -300, \\ ^-400 and AM-500 spectrometer: or Recorded at 400 and 500 MHz on Varian Mercury 400 and INOVA 500 spectrometers. 3C NMR spectra were recorded at 75, 100, or 125 MHz, respectively. 3 proton chemical migration (〇 ') system on Booker AM-300' WH-400 and AM-500 spectrometers, or at ι〇 (^ 125 megahertz recorded on Weirance 400 and Innova 500 spectrometers, respectively Based on ppm of tetramethylsilane (TMS) Field report, resonance (unless stated otherwise) is recorded using 77.0-ppm CDC13 resonance as the internal standard and reported in ppm according to TMS. Infrared spectrum (IR) is based on Perkin Elmer 1600 series FTIR record green Gas chromatography experiments were performed on a Hewlett-Packard GC model 5890 A equipped with an Alltech column (catalog number 932525, serial number 9059) 25 meters x 0.25 mm diameter x 0.2 mm = gravity Column chromatography 'silica gel plunger and flash chromatography were performed using 230-400 sieve silica gel from EM Scientific, and thin layer chromatography was pre-coated with a layer thickness of 0.25 mm purchased from em Scientific. Silicone 60 F254 glass plate was used. The flame mitigation analysis was performed by Atlanta Microscope Laboratory Company, Georgia 3 0 0 9 1 Norcross P.O. Box 2288. Example 2: General Procedure for Coupling End East Acne and Fang The general procedure for 庠 coupling terminal terminal alkynes and aryl groups is based on a palladium-steel cross-coupling agreement called the Castro-Stephens / Sonogashira Agreement (Sonogashira, K .; Tohda, Y .; Hagihara; N. Tetrahedron Letter (1975 ), 4467. Stephans, R_ D., Castro, CE Journal of Organic Chemistry (1 963), 21, 3313. Suffert, J .; Ziessel, R. Tetrahedral Letter (1991), 32., 757. -21-This paper is sized to the Chinese National Standard (CNS) A4 (210 X 297 mm) ------- install '------- order-------- line < Please read the note on the back first to fill in this page) 463 1 8 3 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs

Blum, J-; Baidossi, W .; Badre, ^ γ .; Hoffmann, R.E .; Shumann, H. Journal of Organic Chemistry (1995), sister, 4738). Equipped with a water-cooled western condenser or screw cap capped pressure tube and a stirring round-bottomed bottle with a stirring rod. Aryl halide, trifluoride (triphenylphosphine) palladium (1 to 3-5 mole%) Halide) and copper (I) iodide (6-10 mole% halide) 3 triphenylphosphine is used in certain reactions to maintain palladium in solution. The container was then sealed with a rubber cap under a nitrogen atmosphere. Cosolvent systems of THF, benzene, or digasmethane are added at this point depending on the degree of aryl i's fall. Then add the base, triethylamine or N'N-diisopropylethylamine and finally add the terminal alkyne (1% Moore% halide) and the reaction is heated to completion. When the reaction is complete, the reaction mixture is quenched with water, a saturated solution of ammonium chloride, or brine. The organic layer was diluted with methane or ether and washed with water, saturated ammonium hydroxide solution or brine (3X). The combined aqueous layers were extracted with chloroform or ether (2x). The organic layers were combined, dehydrated with magnesium sulfate and emptied to remove the solvent to obtain a crude product. The crude product was purified by column chromatography (silica gel). The eluent and other minor modifications are described below for various materials. 3 • Example 3: Trialkylsilyl purge acetylenes are stripped of the protective group—the general procedure is two general methods to protect trialkylsilyl acetylenes. Deprotection 3 According to the first method, the silylated alkyne is dissolved in methanol and potassium carbonate is added. Stir the mixture overnight before pouring into water. The solution was extracted with ether or ethyl acetate and washed with M water = after dehydration with magnesium sulfate, the solvent was removed by evaporation in vacuo to obtain a pure product. According to the second method, the diarrhea block is dissolved in a ρ ratio bite in a plastic container. A mixed solution of 49% hydrofluoric acid and 1.0 M tetrabutylammonium fluoride in THF was added at room temperature. The solution was stirred for 15 minutes and quenched with silicone gel. The mixture was poured into water and the size of the paper was adapted to Chinese National Standard (CNS) A4 (210 X 297 mm). ------ 1 ----- ---- Pack ----(Please read the precautions on the back before filling this page) • ISJ. 4 '463 1 8 3 A7 B7 V. Description of the invention (20 Extraction. The extract was washed with brine and magnesium sulfate After dehydration and filtration, the solvent was evaporated and the solvent was removed. The crude product was purified by flash chromatography on silica gel. The eluent and other minor modifications were described as follows for each material. Example 4: Aryl succinyl thioethionate Cheng Yi added a solution of an aryl halide in THF to a third butyllithium (2 equivalents of halide) in ether (5 ml) at -78 ° C, stirred the slurry for 40 minutes, and added sulfur powder (0.26 g (8.0 ¾ mole) in thF (10 ml) of slurry a. The raw slurry was stirred for 1 hour and then allowed to warm to 0 ° C. The mixture was cooled again to _78 ° F and acetam gas (] .2 equivalents of trioxide) was added. The resulting The yellow solution was allowed to warm to room temperature and stirred for 1 hour before quenching with water. The mixture was extracted with ether (3χ) 3 and the organic portions were washed with water (2χ) Dehydrate with magnesium sulfate. Remove the solvent by emptying and then obtain the required substance after rapid chromatography = eluent and other minor modifications. The description of each material is as follows. 3 Example 2: 2'-amino-m-shiphenylethynyl · 5, -Nitro-1-thioethylfluorenyl fluorene synthesis Synthesis of functionalized conductive pathways used to build molecular-scale devices The description of the synthesis is as follows =-The synthesis procedure is shown in the following reaction diagram: νη2 — — — — — — 1 ^ 1 I-III (Please read the notes on the back before filling this page)

Order --- I • I ti nn Λ Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 68 NHAc 1. Ac? Q. 99¾ / = (— 3 2. HN〇3t H3S〇4.70 ° / d — ~ 卜 BrBr — _Pd / Cu. / -PrNEt. THF y 〆59% o2n

NHAc 69 〇2N 68 K? C05. MeOH, CH2Cl2l 100% Hd ^ u, ι-ΗΐΤΓέ, I Hr, ^

Acs ~ 〇-

o2n 70 nh2 ¢ 15) To synthesize the starting material 2,5-dibromoethyl · anisole, add 2,5-dibromoaniline to a 500 ml round-bottomed bottle equipped with a magnetic stir bar and a Western condenser ( 1.3 8 grams, -23- This paper size is applicable to the National Standard (CNS) A4 specification (210 X 297 mm) 4 63 1 A7 B7 V. Description of the invention (21) 55.0 millimoles, acetic anhydride (50 millimoles) Well) and water (50 ml) were heated at reflux for 12 hours. The resulting mixture was cooled to ambient temperature and poured into water (500 ml). Shen Dian was collected by filtration and further washed with Su 3 to obtain 14.25 g (88% yield) of 2,5-dibromoacetanilide 3. To synthesize 2,5-dibromo-4-nitroethyl aniline ' Dry a 500 ml round-bottomed bottle with a magnetic stir bar. Add sulfuric acid (50 ml) and nitric acid (50 ml) and cool the reaction mixture to 0 ° C. = Compound synthesis process. Care must be taken to ensure that no multiple nitration reactions are performed on the ring Potentially explosive polynitro compound 3 was added with 2,5-dibromoacetanilide (14.25 g, 48.65 mmol) and the reaction mixture was allowed to stir for 2.5 hours. When the reaction was complete, ice (300 g) was slowly added to the reaction mixture. The reaction mixture was filtered and the material needed to collect solid 3 was purified by rapid liquid chromatography, using silica gel as the stationary phase and digas methane as the eluent. The reaction yielded 11.27 g (69% yield) of 2,5-dibromo- 4-nitroacetamidine. In order to synthesize 2-bromo-4-nitro-5- (phenylethynyl) acetanilide: a general procedure using a palladium / copper catalyzed coupling reaction "2,5-dibromo-4-nitroacetamidine ( 3.0 g '8.88 mmoles) was coupled to phenylacetylene (0.98 ml, 8.88 mmoles), and copper iodide osmium (0.17 g, 0.17 g, 0.89 millimolar) vaporized tritium (tribenzylphosphine) she (11) (0.25 g '0.44 millimolar), triphenylphosphine (0.47 g, 1.78 mmol), N, N-diiso Propylethylamine (6.18 ml, 35.52 mmol) and THF (25 ml) were performed. Any reaction mixture was allowed to react at room temperature for 1 day and then heated to 50 ° C for 2 hours = the resulting mixture was subjected to aqueous subsequent treatment as described above. 2-Bromo-4-nitro-5- (phenylethynyl) acetanilide was purified by gravity liquid chromatography, using silica gel as the stationary phase and dioxane as the eluent. The reaction yielded 1.79 g (56.% yield, the first -24- this paper size applies Chinese National Standard (CNS) A4 specifications (210 * 297 mm) ----..-------- ------ • {(Please read the precautions on the back before filling out this page) έ '道 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economy 4 63 1 8 、 A7 _ B7 V. Description of the invention (22) Harvested product) required product. : In order to synthesize 2 -mo-4 -acid-5-(phenylethynyl) aniline, the general procedure for deprotection using trimethylsilyl acetylene is 3 in a 100 ml round bottom bottle equipped with a magnetic stir bar Add 2-O-4-nitro-5- (phenylethynyl) ethyl g aniline (0.33 g '0.92 mmol), potassium carbonate (0.64 g, 4.6 mmol), methanol (15 ml) And methane (15 ml). The reaction was stirred at room temperature for 1 hour == the reaction mixture was quenched with water and extracted with methane (3x). The organic layers were combined and dehydrated with magnesium carbonate. The solvent was removed by emptying. No further purification was required. The reaction gave 0.29 g (100% yield) of 2-bromo-4-nitro-5- (phenylethynyl) aniline as a yellow solid. In order to synthesize 2-amino-4,4-benzylethyl-5'-nitrothioethyl ethylbenzene, a schematic procedure using an ie / copper catalyst coupling reaction was used. 2-bromo-4-nitro-5- (phenylethynyl) aniline (0. to g, 0.30 mmol) was coupled to __thioethenyl-4-ethynylbenzene (0.10 g '0.56 as previously described) Millimoles), a drying round nut equipped with a rod, and a capped pressure tube using copper (I) iodide (0.01 g, 0.03 millimoles), vaporized tritium (three Phenylphosphine) Palladium (11) (0.01 g, 0.02 mmol), triphenylphosphine (0.02 g, 0.06 mmol), N, N-diisopropylethylamine (0,24 ml '1.40 MM) and THF (10 ml). The reaction mixture was allowed to react at 80 ° C for 3 days. The resulting mixture was subjected to the aforementioned aqueous subsequent treatment. 2'-Amine_4,4-diphenylacetylene: yl-5'-nitro-1-thioacetamidine was purified by gravity liquid chromatography using silica gel as the stationary phase and 3: 1 digas. Methane / hexanes are used as eluents. Additional hexane washing was used to obtain 0.80 g of 2, amino-4,4'-diphenylethynyl-5'-nitro-1-thioacetophenone as yellow crystals (67% yield). Example 6: Synthesis of 2'-amino-4.4'-diphenylethynyl-5'-nitrobenzoisonitrile. A molecular scale device with an isonitrile attachment part was synthesized according to the following plan Standards are applicable to Chinese National Standard (CNS) A4 Regulations (210 X 297 Gong) — ---------- Installation— ί (Please read the precautions on the back before filling this page) Order: 463 1 8 2 A7 B7 V. Description of the invention (23. The starting material was prepared as described above in Example 5. Intermediate 69 (2-mo-4-nitro · = (phenylethynyl) acetamidine) amine Partially remove the concealment with potassium carbonate and methanol, and then perform a palladium / copper catalyzed cross-coupling reaction with formamidine-supported compound 84 to obtain compound 85 (2, -amino_4,4, -diphenylethynyl_ 丨 _ Formamidine-5'-nitrobenzyl). This intermediate was found to be insoluble in most semi-solvent systems and was used directly in the next reaction = NHAc 69 0 ^ N νη2

. ^? 00χ MeOH CK.ri-2. WCuf TMSA. Α-Ρ'γ ^ ΝεΓ THF

O '

NHCHO / T-NHCHO o2n BS PPh3. CCU. NEla, CH? Ch S3% (2 steps now)

(23) iTI ---- ml!-Pack ...-- ί (please read the precautions on the back before filling this page) Methylamine on tetragas, carbon, tribenzylphosphine, triethylamine and digas After dehydration in the presence of methane, a molecular scale device 2, -amino_4,4 '· diphenylethynyl_5, and nitropyridine 3 is synthesized as shown below. Intermediate 69 (2-bromo-4-nitro-5- (phenylethynyl) acetamidine) was synthesized as in Example 5. In order to synthesize 2, _amino_4,4, · diphenylethynyl_ 丨 _formamidine. 5'-nitrobenzene, a general procedure using a palladium / copper catalyzed coupling reaction. 2-Bromo_4_ethynylphenyl-5-nitroaniline (69) (0.26 g, 0.83 mmol) was coupled to 1-ethynyl-4-methylamidobenzene (85) (0.15 g) as previously described , 1.00 millimolar), in a capped pressure tube equipped with a magnetic stirrer, use copper (1) (0.02 g, 0.08 millimolar) gasified amine (triphenylphosphine) to put (n) (0.03 g, 0.04 mmol), ~~ diisopropylethylamine (0.58 ml, 3.32 mmol) and butyl (25 ml) were carried out 3 reaction mixture was stirred at 705C for 3 Said. The resulting mixture is subjected to the above-mentioned aqueous subsequent treatment 3 2. Amine-4,4'-diphenylethynyl-5'-nitrobenzene Borrowed weight 26 This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) ) -5J · 'Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 4 6

V. Description of the invention (24 force liquid chromatography purification, using silica gel as a stationary phase and 1: 1 ethyl acetate / hexanes as a bath ionizer. Additional purification using gravity liquid chromatography, using stone gum As a stationary phase and an ethyl acetate mixture as a dissolving agent a, 0.23 g of an impure product was obtained. The pure product was subjected to the next synthetic step. In order to synthesize 2'-amino-4,4'-dibenzylethoxy-5, Nitrophenylacetonitrile (86), 2'-amino-4,4'-diphenylethynyl · 5, _nitro Benzene (85) (0.04 g, 010 mmol), triphenylphosphine (0.09 g, 0.33 mmol), triethylamine (0.04 ml, 0.39 mmol) , Tetragasified carbon (0.03 ml, 0.31 mmol) and dichloromethane · pit U (0 ml). The reaction was heated to 60 ° C for 5 hours. The reaction mixture was cooled and burned with water, and extracted with dioxane (3 x). The 3 organic layers were combined and watered with magnesium. The crude reaction mixture was emptied to remove volatiles. 3 The crude reaction mixture was purified by gravity liquid chromatography, using silica gel as the stationary phase and ethyl acetate as the eluent. Additional purification was performed using gravity liquid chromatography, using silica gel as the stationary phase and i: [digas methane / hexane mixture as eluent. The reaction yielded 0.3 g (83% yield '2 steps) of 2'-amino-4,4'-diphenylethynyl-5'-nitrophenylacetonitrile = Example. Example 7: ethynyl, nitro- 1 ethynyl group-1-(sulfur --- rr ---------- device-ί (please read the precautions on the back first and fill in this page) -έτΒΙ, I. Ministry of Economic Affairs The Intellectual Property Bureau employee consumer cooperative prints Ethyl) In order to determine the effect of the electronic withdrawal part on the electrical properties of the compound, the material contains a nitro part. Synthesis No. 2 76 1.Pd / Cu.TMSA, ^ NEl. THF TPdTCu.f-Pr ^ Ntt.T Hr

TMS 26% 1. K? CO ^, MeOH. CHgCl? -PdiCu. ^ Pr2NE \. THr I— ¢ ^^)-SAc N〇2

SAc (19) 27- 19e This paper size is applicable to the Chinese family standard (CNS) A4 specification (21 × 297 mm) 463 1 8 3 A7 ___B7___ V. Description of the invention (25) (Please read the notes on the back before filling in (This page) 2,5-Dibromonitrobenzene is then catalyzed by palladium / copper with trimethylsilylacetylene to become a more reactive bromide, ortho to the nitro moiety, and then coupled to phenylacetylene Intermediate (77) was obtained. The terminal acetylene was deprotected and then coupled to 1-iodo-4-thioacetamidinylbenzene (3) to obtain a molecular scale device (78). The details of the synthesis are as follows. In order to synthesize 1-bromo-3 · nitro-4- (trimethylsilylethynyl) benzene, a general procedure using a palladium / copper catalyzed coupling reaction. 2,5-dibromonitrobenzene (1.77 g, 4.89 mmol), gaseous europium (tribenzylphosphine) palladium (11) (〇πg, 025 mmol) (1) (0.09 grams, 0.49 millimoles) and stir bar are added to dry large nut tube = air is removed and backfilled with nitrogen (3 times). THF (30 ml), HGnig base (3.41 ml, 19.56 mmol) and trimethylsilylethane (0.69 ml, 4.9 mmol) were then added via a syringe under nitrogen. The tube was capped and heated to 70 ° C in an oil bath. After 18 hours, the reaction flask was cooled to room temperature and the total solution was evaporated with a gas solution. The organic product is extracted by gasification and solution and digassing. 3 Because the product is difficult to separate ', complete separation is not achieved, so the resulting mixture continues to the next reaction step. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. In order to synthesize 1-nitro-2- (trimethylsilylethynyl) _5_ (benzylethynyl) benzene, a general procedure using palladium / copper catalyzed coupling reaction. Gadolinium (triphenylphosphine) Ibarium (Π) (0.14 g, 0.20 mmol), copper iodide (ι) (〇07 g, 0.40 mole) and stir bar were added to the oven Dry large nut inside the tube. The reaction mixture from the previous reaction was placed in a small flask and air was removed and backfilled with nitrogen (3 times). Distilled butyl Hf was used to dissolve the mixture in the flask while transferring the resulting solution through a syringe into a screw cap tube under nitrogen 3 then Hanning's base (2 79 ml, 16.6 mmol) and phenylacetylene ( 0.57 ml, 5.2 millimoles) via a syringe with a screw cap 3 -28- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs Consumer Cooperative 463 1 8 3 A7 --------- B7________ V. Description of the invention (26) The tube is capped and heated in an oil bath to 7 (rc ^ After 3 days, the reaction tube is cooled to room temperature and quenched by gasification as a solution And three-column chromatography with thick reddish brown oil extraction with digas methane extraction (2: 1 hexane / digas methane was used as the eluent for silica gel) to obtain the desired product (0.172 g, 26% yield). In order to synthesize 1-nitro-2- (ethynyl) _5- (phenylethynyl) benzene, a general deprotection procedure for protecting acetylene with trimethyl crushed alkyl group. Nitro_2_ (trimethylsilylacetylene) ) -5 · (phenylethynyl) benzene (〇17g, 053mmol) using potassium carbonate (0.36g, 2.6mmol) , Methanol (10 ml) and digas methyl alcohol (10 ml) were deprotected to become terminal alkyne. The mixture in the round bottom flask was stirred at room temperature for 2 hours. The product was extracted according to the foregoing procedure to obtain 0.88 of the desired product. It is immediately followed by Step 3 for the synthesis of 4- (4'-phenylethlyl) _2'_nitro- 丨 '_ (ethynyl) phenyl-1- (thioethylfluorenyl) benzene' 'using palladium / Copper-catalyzed coupling reaction procedure. 1 _Nitro-2- (ethynyl) -5- (phenylethynyl) benzene (013 g) uses the aforementioned palladium / copper cross coupling to couple 4-thioacetamidinium iodide Benzene (〇 · 丨 9g, 0.88 mol), the reaction is in a dry nut tube under nitrogen using gaseous thallium (triphenylphosphine) palladium (11) (0.0 19 g, 0.026 mmol) Ear), copper iodide (1) (0.01 g, 0.05 mol), THF (30 ml) and Hanning's base (0.36 7 ml, 2.10 mmol) were performed in 3 test tubes at 6 (Stir in the TC oil bath for 23 hours.) Then the test tube was cooled to room temperature and quenched and extracted as before. Column chromatography (silica gel, using 1: 1 hexanes / digas methane as eluent) to obtain the desired product (0.040 g Two steps (18.8% yield) was obtained as a yellow solid. Example 7: I (V) molecular electronic device characteristics The negative differential resistance (NDR0) of the specific molecular device described here was studied. -29- This paper scale applies Chinese national standards (CNS) A4 specification (210 X 297 mm) ---------------------- ^ --------- 1 '< Please first Read the note i on the back and fill in this page) 463183 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 ---------------- 5. Description of Invention (27) The starting substrate is a 250-micron-thick double-sided polished silicon (100) wafer. Low-pressure chemical vapor deposition (Lpc VD) is used to deposit 50 nanometers of low-stress ShN4 on the reverse side by photolithography and reactive ions. Etching (R [E) removes 400 μm x 400 μm square nitride. Exposure of silicon to direction-dependent anisotropy. Etching (5 // potassium hydroxide solution at 85.0) etched through to the top surface, leaving a suspended 40 micron x 40 micron silicon nitride film. Single holes with a size of 30-50 nm were made through the film by electron beam lithography and RIE. Due to the strain geometry, the RIE rate is substantially reduced, so the distal opening is much smaller than the actual patterned size, resulting in a niobium geometry cross section. A metal contact with a thickness of 200 nm was deposited on the top surface of the film and the film hole was filled with gold. The sample was then immediately transferred to 2, _amino_4_ ethynylbenzyl-4'-ethynylphenyl_5, nitro_ 1_ (thioethenyl) benzyl (0.5 mM in THF) and Ammonium hydroxide (concentrated aqueous solution, 5 µl / mg bu (thioethylammonium) benzene) was self-assembled under an inert atmosphere of argon for 4S hours. The sample is then cleaned and quickly loaded into the hollow chamber and set up on a liquid nitrogen cooling platform for electronic gold deposition on the bottom surface. The 200 nm gold is deposited at 77 degrees K at a rate of less than 1 angstrom per second = then The device is cut into individual wafers, adhered to the envelope and loaded into a variable temperature cryostat (Janis) for measurement using an HP4145 semiconductor parameter analyzer. A series of control experiments were performed on SAM using alkanethiol-derived conductive paths, using silicon nitride films without porous silicon and films with pores but without conductive paths. Gold-alkanethiolate-gold and gold-silicon nitride film-gold junctions show room-temperature and low-temperature (60K) bipolarity display current levels that are dependent on the noise limit of the device (below 1 picoampere) . Devices containing SAM conductive paths but without nitro or amine functional groups do not have negative differential resistance performance under similar experimental conditions. 3 -30- This paper size applies to China National Standard (CNS) A4 specifications (2〗 0 X 297 public Love) — Jiillllllln ill —---- 丨 Order --------- ^ < Please read the notes on the back before filling in this page) 4631 8 3 A7 B7 V. Description of the invention () Figure 8 is gold -(2'-Amino-4 -ethynylbenzyl_4, _ethynylphenyl · 5 '· nitro-phenylbenzenethiol) -of a gold molecular electronic device; [(v) characteristic s measuring system At 60 degrees. When the bias sweep direction changes, the current versus voltage plot can be completely inverted. The positive bias corresponds to the hole injection of the thiol end of the conductive path and the electron injection from the end of the vapor deposition contact. The peak-to-valley ratio (PVR) exceeds 103. This performance exceeds the performance observed in a typical solid-state quantum well resonance tunneling heterogeneous structure. The PVR characteristic of this device, due to the typical leakage current of silicon nitride, can be larger than the number reported here. Figure 9 shows the (V, T) characteristics of the gold- (2, -amino-4 · ethynylbenzyl-4, ethynylbenzyl-5, _nitro-bubenthiol ester) -gold device. 3This device has + voltage position and current amplitude shift with time, as shown in Figure 9. : Yu / Heptasonic electronic device observes the high-conductivity signal body visits the factory as described in Example 7 'Compound 2, -amino-4,4, -diphenylethynylnitro-1 -phenylthiolate binding Nano-pores at gold contacts. The initial low-conductivity state was written as a high-conductivity state when an applied voltage spike was applied. Figure 丨 0 shows the beginning of gold- (2'-amino-4,4'-diphenylethynyl-5, -nitro- 丨 _phenylthiolate) -gold at 200 degrees K (defined as " 〇 ”) and the 1 (V) characteristic after the write pulse (defined as“ 1 ”) and the difference between the two states (defined as“ 1 ”-Γ 0”) ° These characteristics are at low bias and high temperature Measure. The positive bias corresponds to the hole injected from the thiol-gold contact. The device initially showed low conductivity using positive voltage detection. The subsequent positive sweep shows a highly conductive state, and the l (v) characteristic is the same as the previous number 値 (Γ 1 ″). Sweeping the baboon in the opposite bias direction causes the bias voltage to be reset to 1 (V) in the same way as the initial value ("0" in this example). 1 (V) characteristics. -31-This paper size is applicable to China National Standard (CNS) A4 (210 X 297 public love) I ---------- Loading--t Please read the precautions on the back and fill in this page first ) Order.-Line / Printed by the Employees' Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs and printed by the Employees' Cooperatives of the Ministry of Economic Affairs and the Intellectual Property Bureau's printed by employees' cooperatives 463183 A7 V. Description of the invention (29) Figure 1 1 _4,4, diphenylethynyl-5, -nitro · I-stupolate) -gold) the difference characteristics ("1" · "〇") as a function of temperature difference / watt Research; the range decreases approximately linearly with increasing temperature. 'Bit element has the inter-temporal characteristic bit retention time is the gold of Example 7_ (2, _amino-4,4'-diphenylethyl block-5'-nitrobenzenethiol ester) _Measured the stored 鬲 conductive state at different time intervals after the gold program planning. It is learned that after the initial write bias sweep, the peak current of the stored state "I" has an exponential decay and the time constant (7) is 2 6. The degree κ is 790 seconds. As shown in FIG. 12a, the measurement of the bit retention time at different temperatures shows an exponential dependency on 丨 / T 'to indicate activation performance, as shown in Figure 丨 3. This behavior can be expressed by r = τ. The active energy of this bias scheme is about 76 ± 7 me V for this system. Observation of the low-thunder lightning memory effect of electronic devices & material 4,4-monophenylethynyl_2'-nitro_I · phenylthiolate as described in Example 7 Within the pores. The initial high-conductivity state is written as a low-conductivity state at the applied voltage pulse. Figure 14 shows that this state is stored in the system at 60 ° κ. Figure 5 shows the storage of this state at 300 degrees κ. The difference between the "0J" and "丨" states is a constant amount of about picoamperes. The window is close to 5 volts, providing a clearly separated threshold. As mentioned above, subsequent read pulses and reset pulses can also restore the I (V) characteristic. 3 The thermal activation at 3 ° K does indeed cause some non-zero “0” current, but the threshold 値 is still clearly separated (200 and 5〇). 〇ί '彳 i 安 间）》 d3L foot point deduction (about 1.5 volts and about 5 picoamperes for "〇", and about U volts and about 100 picoamps for "1") are as follows in Example 丨 1 • 32 · This paper size applies to Chinese National Standards < CNS) A4 specification (21〇x 297 mm) — Loading · --- (Please read the intention on the back ^ Code to complete this page] if '

A Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 463183 A7 --- B7 _ V. Description of the invention (3Q) The operating point of the circuit. Example 11 1: Molecular logic diagram_ Figure 16 is a measurement logic diagram to verify that the random access memory (ram) unit operates at molecular temperature using a molecular scale electronic device. Compound M, diphenylethynyl-2'-ankylo- Benzyl mercaptan is bound to the nanopores of the gold contacts, as described in Example 7. In order to convert the stored conductivity into a standard voltage habit, the output of the device is dropped across a resistor 'and sent to a comparator (set at the point in Figure 15) and inverted and gated using a read pulse. The upper trace shown in Figure 16 is the input waveform applied to the device 'and the lower trace is the RAM unit output. The first positive pulse is written to the bit to configure the state of the unit, and the second and third positive pulses are read from the unit. The third pulse (and subsequent read pulses, not shown in the figure) verifies that the RAM cell is strong and continues to maintain this state. Bits at this temperature have a time limit. Negative pulse erasure bit, reset unit = second set of four pulses repeat this pattern, continuous operation for multiple hours, no observed performance degradation 3 Example 12: Room temperature NDR · ^ 龅 窳 Figure 17 is gold- ( The 4- (ethynylphenyl-4, -ethynylbenzylnitrophenyl thiobenzoate) -gold molecular electronic device is plotted at 300 ° K with its I (V) characteristics. The peak-to-valley ratio (PVR) is smaller than the peak-to-valley ratio of the compound shown in Example 7, but the performance can be sustained at low temperatures. The device has a peak current density of more than 16 amps / cm2, an NDR of less than _144 milliohms cm2, and a PVR of about 1.5: 1 »Figure 18 shows that the device ’s I (V) characteristics at the time of publication = NDR peaks are sharper , PVII is about 4: 1 = The reduction potential difference of this system is also roughly equal to I (V) peak width = Example 1 3: Cyclic Volt Metering of Molecular Scale Devices -33-This paper size applies Chinese National Standard (CNS) A4 specifications ( 210 X 297 males) IJJ--II ----- 丨 -install if --- 丨 1 Order -------- ^ (Please read the precautions on the back before filling this page) 4 63 18 3 A7 _ B7 V. Description of the invention (31 Printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs ^^ 4,4'-Dibenzylethynyl_5, _nitro- 丨 _benzenethiol esters Surgical measurements were performed at room temperature on a B AS CV-50W volt metering analyzer using a silver / silver reference electrode 'dimethylformamide solvent system and M-tetrabutylammonium fluoborate at a scan rate of 10%. Millivolts / second, Figure 9 shows the cyclic volt metering reduction curve 'here the first and second reduction potentials of compound 4,4, -dibenzylethynyl · 5'-nitrophenylthiolate 1 μ volt and 2.3 3 volt = Figure 20 shows the cyclic voltmeter curve of 2'-amino · 4,4, _diphenylethyl block_5, _nitro-benzylthiolate, reduced here The potential spikes are located at 1.4 volts and 2.2 volts, respectively. The reduction potential difference roughly corresponds to the peak width of 1 (V). 2'-amino-4,4, -diphenylethynyl-5'-nitro-phenylthiolate ratio The fact that 4,4'_diphenylethynyl-5, _nitro-N thiothioate is easier to reduce (2, -amino-4,4, -diphenylethynyl-5'-nitrate The reduction potential of the phenyl-thiol ester is lower than the 4,4, -diphenylethynyl-5'-nitro-1-phenylthiol ester by 0.3 volts) due to the 2'_amino group, 4,4-diphenylethynyl-5nitro-benzylthiolate was observed at room temperature n DR, but at 4,4, -diphenylethynyl-5nitro-1 No. Other specific embodiments must understand that although the present invention has been described in detail, the foregoing description is intended to illustrate rather than limit the scope of the invention, which is defined by the scope of the accompanying patent application. Other features, advantages And modifications are within the scope of the following patent applications. Zhang scale applicable Chinese National Standard (CNS) A4 size (210 X 297 mm> Please note entry to read the back of ~% · J St-page book loaded

A

Claims (1)

8 * 1 1.J 6 4 A8B8C8D8 t, patent application scope 1. An electronic device, including: at least two contacts: and (please read the precautions on the back before filling out this page) A single layer of conductive organic material forms a The conductive path is between the contacts, wherein the conductive path includes at least one electron-drawing group. 2. If the device in the scope of the patent application, the device has high and low electrical states 3 3. In the device, the scope of the patent application, the device can be continuously exchanged between high and low conductivity states. 4. If the device in the scope of the patent application, the low conductivity state has a current of less than about 100 picoamperes = 5. If the device in the scope of the patent application, the low conductivity state has a current of less than about 1 picoampere Ann. 6. The device according to item 2 of the patent application range, wherein the conductive state has a current at least about 200 times higher than the low conductive state. 7. The device according to item 6 of the patent application, wherein the conductive state has a current that is at least about 500 times higher than the low conductive state. 8. The device according to item 7 of the patent application, wherein the conductive state has a current which is at least about 1,000 times higher than the low conductive state. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 9- The device of the scope of patent application, wherein the electronic group is selected from the group consisting of cyano, isocyano, nitro, sulfonyl, /?-Carboxyvinyl , Sulfenyl, / 3, / 3-dicyanovinyl, haloalkyl, fluorenyl, carboxyl, carbonyl, alkoxycarbonyl and aryloxycarbonyl, 1-tetrazolyl, 5-Ga-L · The group consisting of tetrazolyl, aminomethylsulfonyl and aminosulfonyl 3 10. As for the device in the scope of application for patent item 9, wherein the electron-drawing group is selected from the group of cyano-35-this paper is applicable to China Standard (CNS) A4 specification (210 X 297 mm) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 4A8 § ___08 VI. Application for a group of patents based on 'isocyano and nitro groups 3 η · as in The material of the first range is as shown in FIG. 1, wherein the electronic group is bonded to the phenyl ring of the conductive path. 12. If the device under the scope of the patent application is applied, the step further includes at least one electron donor. % 13. The device according to item 1 of the patent application range, wherein the conductive path contains atoms, and at least 70% of the atoms are Sp_ or Sp2_ mixed atoms. 14. The device according to the scope of the patent application, wherein the conductive path includes each acetylene group and an aryl group = > ° ^ 1 means the device according to the scope of the patent application, wherein the conductive path includes at least one phenyl group- Ethynyl linkage. Ι. The device according to item 15 of the patent application, wherein at least one of the phenyl groups is substituted with an electron-withdrawing group. 17. The device according to item 1 of the patent application scope, wherein the conductive path further comprises a bonding group which combines the conductive path to the contact. 18. The device according to item 17 of the application, wherein the bonding group is selected from the group consisting of a sulfur atom, an oxygen atom 'cyano, a carboxyl group, a diazonium salt, a halide anion, an isocyano' phosphine group, and a tellurium and i atom Groups of people. 19. If the device of the scope of patent application, the conductive path contains biphenyl group = 20. If the device of the scope of patent application, the conductive path contains ethylenyl group 21. 21. An electronic device, including : Two contacts, at least one of which is a palladium contact; and -36-This paper size applies to China National Standard (CNS) A4 (210x 297 mm) * 7 ---- ^ ------ ---- Equipment --- I ---- Order --------- Line · ί ′ (Please read the notice on the back before writing this page on silicon), the scope of patent application A8B8C8D8- -----Conductive organic molecules that are self-assembled are often repeated. The organic molecules include a phenyl silk group based on materials. The substituted benzene group includes at least one confirmation group, and The organic radical is bonded to the 4e junction by at least one isocyano group on the terminal phenyl group of the linkage. α 22. —A kind of memory circuit, including: a) —Input: b) —Output; The molecular electronic device includes: at least two contacts: and-a single layer of conductive organic material forms a conductive path between the junctions, wherein the conductive path includes at least one electron-drawing base, wherein-the contact bridge wheel: and The output and one of the other contacts are grounded: and a comparator bridges the input and output, where the comparator is a voltage for electrical communication. 23. A kind of memory array, including plural numbers as in the scope of patent application. The memory circuit of the item, wherein the memory circuit is arranged in an addressable array. 24. A kind of static random access memory unit, including: 土 少 / ffr 一一 and ·,! · '* -------- I-装 · — 1 I ---- Order ---- ----- I Γ Please read the notes on the back of the page first to complete this page} The second molecular electronic device printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, each of which includes: at least two contacts: and a single layer The conductive organic material forms a conductive path between the contacts, wherein the conductive path includes at least an electronic base, wherein the first device has a contact connected to a reference voltage, and the other contact is connected to a node, The second device has a contact connected to the ground, and another contact is connected to the node, and the node is further connected to the ground s' 25. For example, the memory unit of the 24th scope of the patent application, where the unit is- 37 A8 4 6 :, 1 D8 6. The scope of patent application includes a gain component. 26. The device according to item 1 of the patent application scope, wherein the device has a negative differential resistance at room temperature. .--- r- > ---------- Installation -------- Order · i (Please read the precautions on the back before filling this page)-Line "Intellectual Property of the Ministry of Economic Affairs The paper size printed by the Bureau ’s Consumer Cooperatives applies the Chinese National Standard (CNS) A4 (210 X 297 mm)