WO2020184662A1 - Dispositif conducteur et diélectrique obtenu à l'aide d'une feuille de bore - Google Patents

Dispositif conducteur et diélectrique obtenu à l'aide d'une feuille de bore Download PDF

Info

Publication number
WO2020184662A1
WO2020184662A1 PCT/JP2020/010807 JP2020010807W WO2020184662A1 WO 2020184662 A1 WO2020184662 A1 WO 2020184662A1 JP 2020010807 W JP2020010807 W JP 2020010807W WO 2020184662 A1 WO2020184662 A1 WO 2020184662A1
Authority
WO
WIPO (PCT)
Prior art keywords
boron
liquid crystal
atomic layer
crystal
layer sheet
Prior art date
Application number
PCT/JP2020/010807
Other languages
English (en)
Japanese (ja)
Inventor
徹也 神戸
伶奈 細野
山下　拓也
笙太郎 今岡
ひなよ 田谷
美沙 清水
山元　公寿
Original Assignee
国立大学法人東京工業大学
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 国立大学法人東京工業大学 filed Critical 国立大学法人東京工業大学
Priority to JP2020540515A priority Critical patent/JP6829920B1/ja
Publication of WO2020184662A1 publication Critical patent/WO2020184662A1/fr

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B35/00—Boron; Compounds thereof
    • C01B35/08—Compounds containing boron and nitrogen, phosphorus, oxygen, sulfur, selenium or tellurium
    • C01B35/10—Compounds containing boron and oxygen
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/10—Inorganic compounds or compositions
    • C30B29/16—Oxides
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G4/00—Fixed capacitors; Processes of their manufacture
    • H01G4/33—Thin- or thick-film capacitors 
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L29/00—Semiconductor devices adapted for rectifying, amplifying, oscillating or switching, or capacitors or resistors with at least one potential-jump barrier or surface barrier, e.g. PN junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof  ; Multistep manufacturing processes therefor
    • H01L29/02—Semiconductor bodies ; Multistep manufacturing processes therefor
    • H01L29/06—Semiconductor bodies ; Multistep manufacturing processes therefor characterised by their shape; characterised by the shapes, relative sizes, or dispositions of the semiconductor regions ; characterised by the concentration or distribution of impurities within semiconductor regions

Definitions

  • the conductive device of the present invention has boron and oxygen as skeleton elements and is networked by a non-equilibrium bond with a boron-boron bond, with an oxygen-boron molar ratio (oxygen / boron) of less than 1.5.
  • this boron layered single crystal can be monolayered by physical and chemical dissolution methods. By applying a physical force to the crystal, a sheet material having a thickness corresponding to a single layer can be obtained on the substrate. Further, this layered single crystal is insoluble in a general aprotic organic solvent, but is dissolved by the addition of cryptondand or crown ether that captures metal ions between layers. In the state where the metal ions are dissolved, it is presumed that the boron sheet is also dispersed in the solution as a single layer.
  • the conductive material When the conductive material is a crystal of the conductive material (1), it exhibits anisotropic conduction. From another point of view, it exhibits anisotropic conduction between and within the crystal planes. Due to these characteristics, the electrode is a conductive device in which a voltage is applied between the crystal planes and the temperature dependence of the conductivity exhibits a semiconductor-like behavior, and the electrode applies a voltage in the crystal plane to the temperature of the conductivity. Provided are a conductive device or the like whose dependence exhibits metallic behavior.
  • (A) is a schematic view of the vertical cross section of the dielectric device of the example and the hot plate for heating
  • (b) is a photograph of the actually manufactured dielectric device viewed from above. It is a cycle characteristic of the dielectric constant ⁇ r'of the boron liquid crystal during the heating and cooling process of the dielectric device of the example. 275 ° C., at 100 mV, the frequency is the frequency dependence of the dielectric constant of the boron liquid crystal epsilon r 'between 20Hz ⁇ 10 6 Hz.
  • (A) is the dielectric constant ⁇ r'of the boron liquid crystal during the heating and cooling processes
  • (b) is the DSC curve of the boron liquid crystal under vacuum conditions in the glass capillary.
  • component Y is a boron oxide moiety containing B—OH.
  • the component Y is a site whose structure is similar to trivalent B 2 O 3 and B (OH) 3 (FIG. 3 (b)), and the binding state of BO is different from that of the skeletal site. According to the identification by measurement of the boron layered crystal containing this atomic layer sheet, it is as follows.
  • the amount of at least one selected from crown ether and cryptondand is not particularly limited, but an amount that is excessive with respect to the laminated sheet is preferable.
  • thermotropic liquid crystal maintains a liquid crystal state in a temperature range of at least -196 to 350 ° C.
  • the interference color of the liquid crystal phase I is stably shown up to 350 ° C.
  • the cooling process of the liquid crystal phase II to -50 ° C is measured by DSC under argon, other than the phase transition between the liquid crystal phases I and II. No peak is observed on the low temperature side. From this, it is considered that the transition point from the liquid crystal to the crystal exists on the lower temperature side than ⁇ 50 ° C. Further, even if the boron liquid crystal is immersed in liquid nitrogen (-196 ° C.), no change is observed in the liquid crystal structure.
  • thermotropic liquid crystal When this thermotropic liquid crystal is produced by heating crystals to 100 ° C. or higher, the distance between atomic layer sheets increases due to the heating.
  • the boron sheet structure of the liquid crystal phase II contains components in the c-axis direction, which is the stacking direction, and the peaks of (001), (101), and (111) are on the lower angle side than the crystal before heating.
  • the interplanar spacing (001), which indicates the layer spacing is 3.47 ⁇ in the crystalline state, whereas it is 3.54 ⁇ in the liquid crystal phase II, which is about 0. It is expanding by 1 ⁇ .
  • B (OH) 3 is a molecule with a perfect planar structure, but it has a three-dimensional tetrahedral structure by dehydration condensation and conversion to B 2 O 3 . Therefore, it is considered that B (OH) x on the plane of the boron sheet end / defect site also undergoes a three-dimensional structural change by dehydration condensation with the adjacent end in the sheet. It is considered that such changes in the ends and defects that break the stacking of the sheets create fluidity between the sheets and develop liquid crystallinity. It is considered that the reason why the transition from the liquid crystal to the crystal is not observed even if the boron layered crystal is once liquid crystallized and then cooled is because the dehydration condensation between B and OH that produces the liquid crystal state is irreversible.
  • the lyotropic liquid crystal in the present invention includes the atomic layer sheet described above.
  • a laminated sheet containing metal ions between a plurality of atomic layer sheets is included.
  • the details of the atomic layer sheet, the laminated sheet, the metal ion, and the like in the lyotropic liquid crystal of the present invention are as described above, and the description thereof will be omitted.
  • the electrode may be conducted by forming an electrode on a separate base material and physically contacting the electrode with the conductive material (1), or by forming the electrode directly on the surface of the conductive material (1). May be good.
  • the method for forming the electrode is not particularly limited, but for example, the electrode can be formed by a method such as vapor deposition or sputtering, and can be patterned into a desired shape by lithograph or etching treatment. Further, when the electrode is formed by using the conductive polymer or the conductive fine particles, the solution or dispersion of the conductive polymer or the dispersion of the conductive fine particles may be patterned by an inkjet method from the coating film. It may be formed by lithograph, laser ablation, or the like.
  • the conductive device includes a conductive material (2) including the atomic layer sheet described above, and an electrode to which a voltage is applied.
  • the electrodes are connected to a power source that applies voltage and / or current to the conductive material (2), such as a DC power source or an AC power source, to form a device.
  • a liquid crystal can be accommodated in a two-dimensional manner using an accommodating body such as a liquid crystal cell, and electrodes can be arranged on both sides thereof.
  • a transparent conductive film such as indium tin oxide alloy (ITO), tin oxide (NESA), zinc oxide (IZO), etc. may be formed on a transparent substrate such as glass, and this substrate may be arranged on a liquid crystal surface. it can.
  • the conductive device of the present invention using the conductive material (2) is expected to be industrially used in various technical fields such as nanocoils, nanocircuits, and light control films.
  • a single layer of the atomic layer sheet or a solution of a laminated sheet containing the atomic layer sheet and metal ions between the atomic layer sheets in a solvent is applied in a thin film form. It is a thin-layer sheet from which the solvent has been removed.
  • These forming methods are not particularly limited, but can be obtained, for example, by thinly applying the above-mentioned lyotropic liquid crystal composition to a substrate such as a plate and then removing the solvent.
  • Such a conductive material (3) is typically a thin film having a sheet having a single atomic layer to several layers as a main component.
  • the relative permittivity of most liquid crystals is about 2 to 3.
  • the relative permittivity of the thermotropic liquid crystal which is a dielectric material, is 10 or less, for example, about 2 to 3, which is equivalent to that of a general liquid crystal when the liquid crystal phase II is used, while the liquid crystal phase I when the, dramatically increased for example up to more than 10 5.
  • the dielectric device is not particularly limited, and examples thereof include a capacitor, an inductor, a transmission line, a dielectric filter, a dielectric antenna, and a dielectric resonator.
  • a capacitor an inductor
  • a transmission line a dielectric filter
  • a dielectric antenna a dielectric antenna
  • a dielectric resonator a dielectric resonator
  • the dielectric device When the means is an electrode, the dielectric device typically applies a dielectric material and a voltage and / or current from a power source to the dielectric material, or a voltage and / or current to the dielectric device.
  • a plurality of electrodes for supplying to the outside are electrically connected.
  • a pair of electrodes are electrically connected with a dielectric material interposed therebetween.
  • Specific examples include a MIM (Metal-Insulator-Metal) capacitor in which a dielectric material is sandwiched between electrodes.
  • the above-mentioned fluid thermotropic liquid crystal may be accommodated and sealed to maintain a constant shape.
  • the dielectric device may further include an electrode, and the electrode is in the manner described above. It is electrically connected to the dielectric material.
  • thermotropic liquid crystal a phase reversible phase transition with respect to temperature is controlled between the liquid crystal phase I on the high temperature side and the liquid crystal phase II on the low temperature side, thereby controlling the phase transition between them.
  • a device for controlling the temperature which can reversibly express and control the relative dielectric constants of the different liquid crystal phases I and II, may be installed.
  • the dark part of the cross is visible on the peripheral edge because the optical axis of the liquid crystal domain is oriented along the direction of the orthogonal polarizing plate, and the polarized light is transmitted as it is without interfering with it. Therefore, it is considered that the boron sheets are concentrically oriented in the liquid crystal.
  • the weight loss of about 19% near the liquefaction temperature observed by the TG measurement is more than 5 times the value when it is assumed that the ends of the boron sheet and the defective sites are all dehydrated and condensed. It can also be seen that the decrease starts from the low temperature side as compared with the dehydration temperature of B (OH) 3 .
  • this weight loss as a result of creating a differential curve for the weight loss of TG near 100 ° C, it can be separated into two stages of weight loss, a broad decrease from around 75 ° C and a sharp decrease around 125 ° C. I understand (Fig. 17 (a)).
  • the Seebeck coefficient of boron crystals is much larger than that of general semiconductors, and the carrier concentration is considered to be low.
  • Dielectric device using boron layered liquid crystal and permittivity measurement A device was manufactured to measure the dielectric constant of boron liquid crystal using electrodes.
  • the boron crystal synthesized above was sandwiched between electrodes, and only one side was left and fixed with a bond to create an argon atmosphere, which was further vacuum-heated to form a liquid crystal (1st heating). Then, the remaining one side under anaerobic conditions was sealed by fixing with a bond.
  • the electrode arrangement in which the boron crystal is sandwiched between the pair of upper and lower substrates is that the boron crystal is sandwiched between the electrode surfaces in the center of the substrate and the upper and lower connecting portions are arranged along the opposite substrate end faces. The upper and lower connecting parts were shifted so that the surface was exposed to the outside, and the upper and lower boards were fixed.
  • the polarization of a dielectric can be divided into electronic polarization, ionic polarization, orientation polarization, and interfacial polarization based on four different polarization mechanisms. It is considered that the boron liquid crystal is oriented according to the electric field because the domain can move freely at high temperature, the distance between the sheets is extended, and ionic polarization by the anion sheet and potassium ion is generated to obtain a high dielectric constant. As the result of the XRD measurement, the interplanetary distance is longer than that of the crystal, so it is considered that a space where the cation (K + ) can move freely is created and a large polarization occurs. As described above, it showed a large dielectric constant boron crystal exceeds 10 5 over a wide frequency has a high thermal stability. Taking advantage of these characteristics, it is expected to lead to application to materials such as capacitors, sensors, and liquid crystal displays under extreme conditions.
  • CsBH 4 (Cs boron layered crystal) CsBH 4 was added to 40 ml of the solvent MeCN in a glove box in an argon gas atmosphere. The concentration of CsBH 4 was 8 mM.

Abstract

L'invention concerne un dispositif conducteur obtenu à l'aide d'un cristal liquide cristallin ou thermotrope qui comprend une feuille de couche atomique, qui contient du bore et de l'oxygène en tant qu'éléments de structure, dans lequel un réseau est formé par liaison hors-équilibre ayant des liaisons bore-bore, et dans lequel le rapport molaire de l'oxygène et du bore (oxygène/bore) est inférieur à 1,5, ou comprend une feuille stratifiée contenant une pluralité de feuilles de couche atomique et des ions métalliques entre les feuilles. L'invention concerne également un dispositif diélectrique obtenu à l'aide du cristal liquide thermotrope.
PCT/JP2020/010807 2019-03-14 2020-03-12 Dispositif conducteur et diélectrique obtenu à l'aide d'une feuille de bore WO2020184662A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2020540515A JP6829920B1 (ja) 2019-03-14 2020-03-12 ホウ素シートを用いた導電性および誘電体デバイス

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2019-047639 2019-03-14
JP2019047639 2019-03-14

Publications (1)

Publication Number Publication Date
WO2020184662A1 true WO2020184662A1 (fr) 2020-09-17

Family

ID=72426774

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2020/010807 WO2020184662A1 (fr) 2019-03-14 2020-03-12 Dispositif conducteur et diélectrique obtenu à l'aide d'une feuille de bore

Country Status (2)

Country Link
JP (1) JP6829920B1 (fr)
WO (1) WO2020184662A1 (fr)

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2018050052A (ja) * 2013-05-09 2018-03-29 サンエディソン・セミコンダクター・リミテッドＳｕｎＥｄｉｓｏｎ Ｓｅｍｉｃｏｎｄｕｃｔｏｒ Ｌｉｍｉｔｅｄ 基板上の窒化ホウ素およびグラフェンの直接および連続形成

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2018050052A (ja) * 2013-05-09 2018-03-29 サンエディソン・セミコンダクター・リミテッドＳｕｎＥｄｉｓｏｎ Ｓｅｍｉｃｏｎｄｕｃｔｏｒ Ｌｉｍｉｔｅｄ 基板上の窒化ホウ素およびグラフェンの直接および連続形成

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
LUO, W. W. ET AL.: "The adsorption and dissociation of oxygen on Ag(III) supported x3 borophene", PHYSICA B: CONDENSED MATTER, vol. 537, 31 January 2018 (2018-01-31), pages 1 - 6, XP085365832 *
ZHANG, RUIQI ET AL.: "Two-Dimensional Stoichiometric Boron Oxides as a Versatile Platform for Electronic Structure Engineering", JOURNAL OF PHYSICAL CHEMISTRY LETTERS, vol. 8, no. 18, 2017, pages 4347 - 4353, XP055629710, DOI: 10.1021/acs.jpclett.7b01721 *

Also Published As

Publication number Publication date
JP6829920B1 (ja) 2021-02-17
JPWO2020184662A1 (ja) 2021-03-18

Similar Documents

Publication Publication Date Title
Liu et al. Composite-hydroxide-mediated approach for the synthesis of nanostructures of complex functional-oxides
Chandran et al. Preparation and characterization of MgO nanoparticles/ferroelectric liquid crystal composites for faster display devices with improved contrast
Tholkappiyan et al. Investigation on spinel MnCo 2 O 4 electrode material prepared via controlled and uncontrolled synthesis route for supercapacitor application
Li et al. Solvothermal elemental direct reaction to CdE (E= S, Se, Te) semiconductor nanorod
Zhang et al. A general strategy toward transition metal carbide/carbon core/shell nanospheres and their application for supercapacitor electrode
Zhang et al. Facile preparation, optical and electrochemical properties of layer-by-layer V2O5 quadrate structures
Asiya et al. Reliable optoelectronic switchable device implementation by CdS nanowires conjugated bent-core liquid crystal matrix
CN102583340B (zh) 低温气相还原的高导电石墨烯材料及其制备方法
Marx et al. Bent-core liquid crystal (LC) decorated gold nanoclusters: synthesis, self-assembly, and effects in mixtures with bent-core LC hosts
Yang et al. The hydrothermal synthesis and formation mechanism of single-crystalline perovskite BiFeO 3 microplates with dominant (012) facets
Nithiyanantham et al. Shape-selective formation of MnWO 4 nanomaterials on a DNA scaffold: magnetic, catalytic and supercapacitor studies
Pal et al. CdS nanowires encapsulated liquid crystal in-plane switching of LCD device
Pal et al. Switching of ferroelectric liquid crystal doped with cetyltrimethylammonium bromide-assisted CdS nanostructures
Alsawafta et al. Improved electrochromic properties of vanadium pentoxide nanorods prepared by thermal treatment of sol-gel dip-coated thin films
Zhao et al. ZnTeMoO 6: a strong second-harmonic generation material originating from three types of asymmetric building units
Hameed et al. Synthesis of Sm3+ and Gd3+ ions embedded in nano-structure barium titanate prepared by sol-gel technique: terahertz, dielectric and up-conversion study
Teli et al. Effect of thermal annealing on physiochemical properties of spray-deposited β-MnO2 thin films for electrochemical supercapacitor
Roy et al. Template free synthesis of CdSnO3 micro-cuboids for dye sensitized solar cells
Zhao et al. Hexagonal and prismatic nanowalled ZnO microboxes
Peksa et al. Revisiting a perovskite-like copper-formate framework NH4 [Cu (HCOO) 3]: order–disorder transition influenced by Jahn-Teller distortion and above room-temperature switching of the nonlinear optical response between two SHG-active states
Baláž et al. Rapid mechanochemical synthesis of nanostructured mohite Cu 2 SnS 3 (CTS)
Gu et al. Preparation and photoluminescence of single-crystalline GdVO4: Eu3+ nanorods by hydrothermal conversion of Gd (OH) 3 nanorods
Zhang et al. General approach for two-dimensional rare-earth oxyhalides with high gate dielectric performance
JP6829920B1 (ja) ホウ素シートを用いた導電性および誘電体デバイス
Wu et al. Controlled synthesis of multi-morphology Te crystals by a convenient Lewis acid/base-assisted solvothermal method

Legal Events

Date Code Title Description
ENP Entry into the national phase

Ref document number: 2020540515

Country of ref document: JP

Kind code of ref document: A

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 20770086

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 20770086

Country of ref document: EP

Kind code of ref document: A1