KR20100005627A - Bfo based ferroelectric material and manufacturing method thereof - Google Patents

Bfo based ferroelectric material and manufacturing method thereof Download PDF

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KR20100005627A
KR20100005627A KR1020080065732A KR20080065732A KR20100005627A KR 20100005627 A KR20100005627 A KR 20100005627A KR 1020080065732 A KR1020080065732 A KR 1020080065732A KR 20080065732 A KR20080065732 A KR 20080065732A KR 20100005627 A KR20100005627 A KR 20100005627A
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bfo
organic
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mixed solution
rigid
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박병은
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서울시립대학교 산학협력단
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/02—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of inorganic substances
    • H01B3/10—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of inorganic substances metallic oxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
    • H01B3/44—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10B—ELECTRONIC MEMORY DEVICES
    • H10B53/00—Ferroelectric RAM [FeRAM] devices comprising ferroelectric memory capacitors

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Semiconductor Memories (AREA)

Abstract

PURPOSE: A ferroelectric material containing a BFO as a main material is provided to ensure very low leakage current value and low formation temperature, thereby forming a multiferroic material layer of high quality on a silicon substrate. CONSTITUTION: A ferroelectric material containing a BFO as a main material is formed by mixing BFO(BiFeO3) and organic compound. The organic compound is a multiferroic material. The multiferroic material is any one of polyvinylidene fluoride(PVDF), or a polymer, copolymer or terpolymer containing PVDF, or a cyano polymer and its polymer or copolymer.

Description

비에프오를 주성분으로 하는 강유전 물질과, 그 제조방법{BFO based ferroelectric material and manufacturing method thereof}BFO based ferroelectric material and manufacturing method

본 발명은 각종 전기 및 전자 소자의 제조에 효율적으로 사용될 수 있는 강유전 물질에 관한 것으로, 특히 BiFeO3를 주성분으로 하는 강유전 물질과 그 제조방법에 관한 것이다.BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to ferroelectric materials that can be efficiently used in the manufacture of various electrical and electronic devices, and more particularly, to ferroelectric materials containing BiFeO 3 as a main component and a method of manufacturing the same.

일반적으로 다강체라 함은 자발자화(강자성), 자발분극(강유전성) 및 자발변형(강탄성) 특성을 갖는 물질을 칭한다. 이러한 다강체는 초전소자, 압전소자 및 강유전체 메모리 장치의 재료로서 폭넓게 연구되고 있다.In general, a multi-rigid body refers to a material having spontaneous magnetization (ferromagnetic), spontaneous polarization (ferroelectric), and spontaneous deformation (strong elasticity). Such multi-rigid bodies have been widely studied as materials for pyroelectric elements, piezoelectric elements, and ferroelectric memory devices.

이들 다강체로서는 크게 무기물과 유기물로 구분될 수 있다. 무기물 다강체로서는 산화물 다강체, BMF(BaMgF4) 등의 불화물 다강체, 강유전성 반도체 등이 있고, 유기물 다강체로서는 고분자 다강체가 있다.These multi-rigid bodies can be largely divided into inorganic and organic. Examples of the inorganic multi-rigid bodies include oxide multi-rigid bodies, fluoride multi-rigid bodies such as BMF (BaMgF 4 ), ferroelectric semiconductors, and the like.

상기, 산화물 다강체로서는 예컨대 PZT(PbZrxTi1-xO3), BaTiO3, PbTiO3, BFO(BiFeO3) 등의 페로브스카이트(Perovskite) 다강체, LiNbO3, LiTaO3 등의 수도 일메나이트(Pseudo-ilmenite) 다강체, PbNb3O6, Ba2NaNb5O15 등의 텅스텐-청동(TB) 다강체, SBT(SrBi2Ta2O9), BLT((Bi,La)4Ti3O12), Bi4Ti3O12 등의 비스무스 층구조의 다강체 및 La2Ti2O7 등의 파이로클로어(Pyrochlore) 다강체와 이들 다강체의 고용체(固溶體)를 비롯하여 Y, Er, Ho, Tm, Yb, Lu 등의 희토류 원소(R)를 포함하는 RMnO3 등이 있다.Examples of the oxide multi-rigid bodies include perovskite multi-rigid bodies such as PZT (PbZr x Ti 1-x O 3 ), BaTiO 3 , PbTiO 3, BFO (BiFeO 3 ), LiNbO 3 , LiTaO 3, and the like. Pseudo-ilmenite multi-rigid bodies, tungsten-bronze (TB) multi-rigid bodies such as PbNb 3 O 6 , Ba 2 NaNb 5 O 15 , SBT (SrBi 2 Ta 2 O 9 ), BLT ((Bi, La) 4 A multi-rigid body of bismuth layer structure such as Ti 3 O 12 ), Bi 4 Ti 3 O 12 , and a Pyrochlore multi-rigid body such as La 2 Ti 2 O 7 and a solid solution of these multi-rigid bodies And RMnO 3 containing rare earth elements (R) such as Y, Er, Ho, Tm, Yb, and Lu.

또한, 상기 강유전성 반도체로서는 CdZnTe, CdZnS, CdZnSe, CdMnS, CdFeS, CdMnSe 및 CdFeSe 등의 2-6족 화합물이 있다.Examples of the ferroelectric semiconductors include Group 2-6 compounds such as CdZnTe, CdZnS, CdZnSe, CdMnS, CdFeS, CdMnSe, and CdFeSe.

또한, 상기 고분자 다강체로서는 예컨대 폴리비닐리덴 플로라이드(PVDF)나, 이 PVDF를 포함하는 중합체, 공중합체, 또는 삼원공중합체가 포함되고, 그 밖에 홀수의 나일론, 시아노중합체 및 이들의 중합체나 공중합체 등이 포함된다.The polymer multi-rigid body includes, for example, polyvinylidene fluoride (PVDF), a polymer, a copolymer, or a terpolymer containing the PVDF, and other odd nylons, cyano polymers, and polymers thereof. Copolymers and the like.

상기한 다강체에 있어서, 산화물 다강체, 불화물 다강체 및 강유전성 반도체 등의 무기물 다강체는 유기물 다강체에 비하여 다강체 특성이 매우 우수하다. 따라서, 현재 일반적으로 제안되고 있는 압전소자나 초전소자, 강유전성 전계효과 트랜지스터, 강유전체 메모리 등의 경우에는 다강체 물질로서 무기물 다강체의 사용이 우선적으로 고려되고 있다. 특히 무기물 다강체 중에서도 BFO의 경우에는 다강체 특성이 매우 우수하고, 또한 상온에서도 매우 우수한 다강 특성을 나타내기 때문에 압전소자나 초전소자, 강유전성 전계효과 트랜지스터, 강유전체 메모리의 재료 뿐만 아니라 DRAM의 캐패시터 재료로서 주목을 받고 있다.In the multi-rigid body described above, inorganic multi-rigid bodies such as oxide multi-rigid bodies, fluoride multi-rigid bodies, and ferroelectric semiconductors have much superior multi-rigid properties than organic multi-rigid bodies. Therefore, in the case of piezoelectric elements, pyroelectric elements, ferroelectric field effect transistors, ferroelectric memories, and the like, which are currently proposed in general, the use of inorganic multi-rigid bodies is considered as a multi-rigid material. Particularly, among the inorganic multi-rigid bodies, the BFO has excellent multi-rigidity characteristics and shows excellent multi-rigidity characteristics at room temperature. Therefore, as a capacitor material of DRAM as well as piezoelectric element, pyroelectric element, ferroelectric field effect transistor, ferroelectric memory material, etc. It is getting attention.

그러나, 상기한 BFO의 경우에는 다강 특성이 우수한 반면에 누설전류값이 매 우 크고, 또한 이를 이용하여 소자를 제조하는 경우에 그 형성 온도가 매우 높다는 단점이 있다.However, in the case of the BFO, while having excellent multi-steel characteristics, the leakage current value is very large, and when the device is manufactured using the same, the formation temperature is very high.

이에, 본 발명은 상기한 사정을 감안하여 창출된 것으로서, BFO를 주성분으로 하되 누설전류값이 매우 낮고, 또한 그 형성온도가 매우 낮은 BFO를 주성분으로 하는 강유전 물질을 제공함에 그 목적이 있다.Accordingly, the present invention has been made in view of the above circumstances, and an object thereof is to provide a ferroelectric material containing BFO as a main component but having a very low leakage current value and a very low formation temperature.

또한, 본 발명은 상기한 강유전 물질의 제조방법을 제공함에 또 다른 목적이 있다.It is another object of the present invention to provide a method for producing the above ferroelectric material.

상기 목적을 실현하기 위한 본 발명에 따른 BFO를 주성분으로 하는 강유전 물질은 BFO에 대하여 유기물을 혼합하여 구성되는 것을 특징으로 한다.The ferroelectric material based on the BFO according to the present invention for realizing the above object is characterized in that the organic material to the BFO is mixed.

또한, 상기 유기물이 유기물 다강체인 것을 특징으로 한다.In addition, the organic material is characterized in that the organic multi-body.

또한, 상기 유기물 다강체는 폴리비닐리덴 플로라이드(PVDF)와, PVDF를 포함하는 중합체, 공중합체 또는 삼원공중합체, 시아노중합체 및 이들의 중합체나 공중합체 중 하나인 것을 특징으로 한다.In addition, the organic multi-rigid body is characterized in that the polyvinylidene fluoride (PVDF), and a polymer, copolymer or terpolymer, including PVDF, cyano polymer and polymers or copolymers thereof.

또한, 상기 유기물 다강체는 PVDF-TRFE인 것을 특징으로 한다.In addition, the organic multi-rigid body is characterized in that the PVDF-TRFE.

또한, 상기 BFO와 유기물의 혼합물이 용액상태인 것을 특징으로 한다.In addition, the mixture of the BFO and the organic material is characterized in that the solution state.

또한, 상기 혼합용액은 BFO와 유기물 파우더를 혼합한 후, 이를 용매에 녹여서 생성하는 것을 특징으로 한다.In addition, the mixed solution is characterized by producing by mixing the BFO and the organic powder, it is dissolved in a solvent.

또한, 상기 혼합용액이 BFO 용액에 유기물 파우더를 용해시켜 생성되는 것을 특징으로 한다.In addition, the mixed solution is characterized in that it is produced by dissolving the organic powder in the BFO solution.

또한, 상기 혼합용액이 유기물 용액에 BFO 파우더를 용해시켜 생성되는 것을 특징으로 한다.In addition, the mixed solution is characterized in that it is produced by dissolving the BFO powder in an organic solution.

또한, 상기 혼합용액이 BFO 용액과 유기물 용액을 혼합하여 생성되는 것을 특징으로 한다.In addition, the mixed solution is characterized in that it is produced by mixing the BFO solution and the organic solution.

또한, 본 발명의 제2 관점에 따른 다강체층의 제조방법은 BFO와 유기물의 혼합용액을 생성하는 단계와, 상기 혼합용액을 이용하여 기판상에 다강체층을 형성하는 단계 및, 상기 다강체층을 소성하는 단계를 포함하여 구성되는 것을 특징으로 한다.In addition, the method of manufacturing a multi-rigid layer according to the second aspect of the present invention comprises the steps of generating a mixed solution of BFO and organic matter, forming a multi-rigid layer on the substrate using the mixed solution, and the multi-rigid body Firing the layer.

또한, 상기 혼합용액은 BFO와 유기물 파우더를 혼합한 후, 이를 용매에 녹여서 생성하는 것을 특징으로 한다.In addition, the mixed solution is characterized by producing by mixing the BFO and the organic powder, it is dissolved in a solvent.

또한, 상기 혼합용액이 BFO 용액에 유기물 파우더를 용해시켜 생성되는 것을 특징으로 한다.In addition, the mixed solution is characterized in that it is produced by dissolving the organic powder in the BFO solution.

또한, 상기 혼합용액이 유기물 용액에 BFO 파우더를 용해시켜 생성되는 것을 특징으로 한다.In addition, the mixed solution is characterized in that it is produced by dissolving the BFO powder in an organic solution.

또한, 상기 혼합용액이 BFO 용액과 유기물 용액을 혼합하여 생성되는 것을 특징으로 한다.In addition, the mixed solution is characterized in that it is produced by mixing the BFO solution and the organic solution.

또한, 상기 다강체층의 형성은 잉크젯, 스핀코팅법 또는 스크린 인쇄 중 하나를 이용하여 실행되는 것을 특징으로 한다.In addition, the formation of the multi-rigid layer is characterized in that it is carried out using one of inkjet, spin coating method or screen printing.

또한, 상기 기판은 종이, 코딩재가 도포된 종이, 유연성을 갖는 플라스틱 중 적어도 하나를 포함하여 구성되는 것을 특징으로 한다.In addition, the substrate is characterized in that it comprises at least one of a paper, a paper coated with a coding material, a plastic having flexibility.

본 발명에 있어서는 BFO와 유기물의 혼합 용액을 이용하여 다강체층을 형성하게 되므로, 잉크젯, 스핀코팅법 또는 스크린 인쇄 등을 이용하여 용이하게 다강체층을 형성할 수 있게 된다.In the present invention, since a multi-rigid layer is formed by using a mixed solution of BFO and an organic material, the multi-rigid layer can be easily formed using inkjet, spin coating, or screen printing.

또한, 다강체층의 형성온도가 낮아지게 되므로 실리콘 기판상에 고품질의 다강체층을 형성할 수 있게 된다.In addition, since the formation temperature of the multi-rigid layer is lowered, it is possible to form a high-quality multi-rigid layer on the silicon substrate.

또한, 다강체층의 형성온도가 낮아지게 되므로 압전소자, 초전소자, 전계효과 트랜지스터, 강유전체 메모리를 기존의 실리콘 기판 대신에 유기물이나 종이 등과 같은 다양한 종류의 기판 상에 형성할 수 있게 된다.In addition, since the formation temperature of the multi-rigid layer is lowered, the piezoelectric element, the pyroelectric element, the field effect transistor, and the ferroelectric memory can be formed on various kinds of substrates such as organic material or paper instead of the conventional silicon substrate.

또한, 다강체층의 유전율이 매우 높으면서 그 누설전류값이 대폭 낮아지게 되므로 데이터 저장 능력이 우수한 캐패시터를 구현할 수 있게 된다.In addition, since the dielectric constant of the multi-rigid layer is very high and the leakage current value is significantly lowered, it is possible to implement a capacitor having excellent data storage capability.

이하, 본 발명에 따른 실시예를 설명한다. 단, 이하에서 설명하는 실시예는 본 발명의 하나의 바람직한 구현예를 예시적으로 나타낸 것으로서, 이러한 실시예의 예시는 본 발명의 권리범위를 제한하기 위한 것이 아니다. 본 발명은 그 기술적 사상을 벗어나지 않는 범위내에서 다양하게 변형시켜 실시할 수 있다.Hereinafter, embodiments according to the present invention will be described. However, the embodiments described below exemplarily illustrate one preferred embodiment of the present invention, and examples of such embodiments are not intended to limit the scope of the present invention. The present invention can be carried out in various modifications without departing from the spirit thereof.

일반적으로 산화물 강유전체, 불화물 강유전체 및 강유전체 반도체 등의 무기물 다강체는 유기물 다강체에 비하여 유전률이 매우 높다. 따라서, 현재 일반적으로 제안되고 있는 압전소자나 초전소자, 강유전성 전계효과 트랜지스터, 강유전체 메모리 등의 경우에는 강유전체층의 재료로서 무기물 강유전체를 채용하고 있 다.In general, inorganic multi-rigid bodies such as oxide ferroelectrics, fluoride ferroelectrics, and ferroelectric semiconductors have a higher dielectric constant than organic multi-rigid bodies. Therefore, in the case of piezoelectric elements, pyroelectric elements, ferroelectric field effect transistors, ferroelectric memories, and the like, which are generally proposed, inorganic ferroelectrics are used as materials for ferroelectric layers.

그러나, 상기한 무기물 다강체의 경우에는 이를 기판상에 형성할 때 예컨대 500도 이상의 고온처리가 요구된다. 따라서, 다강체층을 실리콘 기판상에 형성하게 되면 고온 공정에서 Pb, Bi와 같은 원소가 실리콘 기판에 확산되는 문제가 발생하게 된다.However, in the case of the inorganic multi-rigid body described above, a high temperature treatment of, for example, 500 degrees or more is required when forming it on a substrate. Therefore, when the multi-rigid layer is formed on the silicon substrate, a problem arises in that elements such as Pb and Bi diffuse into the silicon substrate in a high temperature process.

다강체 중 현재 가장 다강 특성이 우수한 것으로 평가되고 있는 BFO(BiFeO3)의 경우에도 이를 실리콘 기판상에 형성하는 경우에 500도 이상의 고온처리가 요구되고, 이러한 고온 처리에 의해 Bi원소가 실리콘 기판에 확산되는 문제가 발생된다. 또한, BFO의 경우에는 다른 다강체에 비해서 현저히 높은 누설전류값을 갖는다.Even in the case of BFO (BiFeO 3 ), which is currently evaluated to have the most excellent multi-steel characteristics among the multi-rigid bodies, high-temperature treatment of 500 degrees or higher is required when forming it on a silicon substrate. The problem of spreading occurs. In addition, the BFO has a significantly higher leakage current value than other multi-rigid bodies.

따라서, BFO의 경우에는 높은 유전율에도 불구하고 반도체 메모리의 캐패시터 재료로서 사용되기에 많은 단점을 갖고 있다.Therefore, BFO has many disadvantages because it is used as a capacitor material of semiconductor memory in spite of high dielectric constant.

본 발명에 있어서는 BFO에 대하여 유기물을 혼합한 혼합물질을 강유전 물질, 즉 다강체 물질로서 제공한다. 이때, 바람직하게는 유기물로서는 유기물 다강체를 사용할 수 있다.In the present invention, a mixture of organic materials mixed with BFO is provided as a ferroelectric material, that is, a multi-rigid material. At this time, Preferably an organic substance multi-rigid body can be used as an organic substance.

BFO에 대하여 혼합할 수 있는 유기물 다강체로서는 상기한 바와 같이 폴리비닐리덴 플로라이드(PVDF)나, 이 PVDF를 포함하는 중합체, 공중합체, 또는 삼원공중합체가 포함되고, 그 밖에 홀수의 나일론, 시아노중합체 및 이들의 중합체나 공중합체, 바람직하게는 PVDF-TRFE가 사용된다.Examples of the organic multi-rigid body that can be mixed with BFO include polyvinylidene fluoride (PVDF), polymers, copolymers, or terpolymers containing PVDF as described above. Nopolymers and polymers or copolymers thereof, preferably PVDF-TRFE, are used.

또한, BFO에 대하여 혼합할 수 있는 유기물로서는 상기한 유기물 다강체 이외에 일반적인 모노머(monomer), 올리고머(oligomer), 폴리머(polymer), 코폴리머(copolymer)가 사용될 수 있다.In addition, as an organic material that can be mixed with BFO, a general monomer, oligomer, polymer, or copolymer may be used in addition to the above-described organic multi-rigid body.

또한, 상기 유기물로서는 불화 파라-자일렌(fluorinated para-xylene), 플루오로폴리아릴에테르(fluoropolyarylether), 불화 폴리이미드(fluorinated polyimide), 폴리스티렌(polystyrene), 폴리(α-메틸 스티렌)(poly(α-methyl styrene)), 폴리(α-비닐나프탈렌)(poly(α-vinylnaphthalene)), 폴리(비닐톨루엔)(poly(vinyltoluene)), 폴리에틸렌(polyethylene), 시스-폴리부타디엔(cis-polybutadiene), 폴리프로필렌(polypropylene), 폴리이소프렌(polyisoprene), 폴리(4-메틸-1-펜텐)(poly(4-methyl-1-pentene)), 폴리(테트라플루오로에틸렌)(poly(tetrafluoroethylene)), 폴리(클로로트리플루오로에틸렌)(poly(chlorotrifluoroethylene), 폴리(2-메틸-1,3-부타디엔)(poly(2-methyl-1,3-butadiene)), 폴리(p-크실릴렌)(poly(p-xylylene)), 폴리(α-α-α'-α'-테트라플루오로-p-크실릴렌)(poly(α-α-α'-α'-tetrafluoro-p-xylylene)), 폴리[1,1-(2-메틸 프로판)비스(4-페닐)카보네이트](poly[1,1-(2-methyl propane)bis(4-phenyl)carbonate]), 폴리(시클로헥실 메타크릴레이트)(poly(cyclohexyl methacrylate)), 폴리(클로로스티렌)(poly(chlorostyrene)), 폴리(2,6-디메틸-1,4-페닐렌 에테르)(poly(2,6-dimethyl-1,4-phenylene ether)), 폴리이소부틸렌(polyisobutylene), 폴리(비닐 시클로헥산)(poly(vinyl cyclohexane)), 폴리(아릴렌 에테르)(poly(arylene ether)) 및 폴리페닐렌(polyphenylene) 등의 비극성 유 기물이나, 폴리(에틸렌/테트라플루오로에틸렌)(poly(ethylene/tetrafluoroethylene)), 폴리(에틸렌/클로로트리플루오로에틸렌)(poly(ethylene/chlorotrifluoroethylene)), 불화 에틸렌/프로필렌 코폴리머(fluorinated ethylene/propylene copolymer), 폴리스티렌-코-α-메틸 스티렌(polystyrene-co-α-methyl styrene), 에틸렌/에틸 아크릴레이트 코폴리머(ethylene/ethyl acrylate copolymer), 폴리(스티렌/10%부타디엔)(poly(styrene/10%butadiene), 폴리(스티렌/15%부타디엔)(poly(styrene/15%butadiene), 폴리(스티렌/2,4-디메틸스티렌)(poly(styrene/2,4-dimethylstyrene), Cytop, Teflon AF, 폴리프로필렌-코-1-부텐(polypropylene-co-1-butene) 등의 저유전율 코폴리머 등이 사용될 수 있다.In addition, as the organic material, fluorinated para-xylene, fluoropolyarylether, fluorinated polyimide, polystyrene, poly (α-methyl styrene) (poly (α) -methyl styrene), poly (α-vinylnaphthalene), poly (vinyltoluene), polyethylene, cis-polybutadiene, poly Propylene, polyisoprene, poly (4-methyl-1-pentene), poly (tetrafluoroethylene), poly ( Chlorotrifluoroethylene (poly (chlorotrifluoroethylene), poly (2-methyl-1,3-butadiene) (poly (2-methyl-1,3-butadiene)), poly (p-xylylene) (poly ( p-xylylene)), poly (α-α-α'-α'-tetrafluoro-p-xylylene) (poly (α-α-α'-α'-tetrafluoro-p-xylylene)), poly [1,1- (2-methyl propane) bis (4-phenyl) carbonate] (poly [1,1- (2-methyl propane) bis (4-phenyl) carbonate]), poly (cyclohexyl methacrylate), poly (chlorostyrene), poly (2,6- Dimethyl-1,4-phenylene ether) (poly (2,6-dimethyl-1,4-phenylene ether)), polyisobutylene, poly (vinyl cyclohexane), Nonpolar organics such as poly (arylene ether) and polyphenylene, poly (ethylene / tetrafluoroethylene), poly (ethylene / chloro Poly (ethylene / chlorotrifluoroethylene), fluorinated ethylene / propylene copolymer, polystyrene-co-α-methyl styrene, ethylene / ethyl Ethylene / ethyl acrylate copolymer, poly (styrene / 10% butadiene) (poly (styrene / 10% butadiene), poly (styrene / 15% butadiene) (po ly (styrene / 15% butadiene), poly (styrene / 2,4-dimethylstyrene) (poly (styrene / 2,4-dimethylstyrene), Cytop, Teflon AF, polypropylene-co-1-butene (polypropylene-co- Low dielectric constant copolymers such as 1-butene) and the like can be used.

그리고, 그 밖에 폴리아센(polyacene), 폴리페닐렌(polyphenylene), 폴리(페닐렌 비닐렌) (poly(phenylene vinylene)), 폴리플루오렌(polyfluorene)과 같은 공액 탄화수소 폴리머, 및 그러한 공액 탄화수소의 올리고머; 안트라센(anthracene), 테트라센(tetracene), 크리센(chrysene), 펜타센(pentacene), 피렌(pyrene), 페릴렌(perylene), 코로넨(coronene)과 같은 축합 방향족 탄화수소 (condensed aromatic hydrocarbons); p-쿼터페닐(p-quaterphenyl)(p-4P), p-퀸쿼페닐(p-quinquephenyl)(p-5P), p-섹시페닐(p-sexiphenyl)(p-6P)과 같은 올리고머성 파라 치환 페닐렌 (oligomeric para substituted phenylenes); 폴리(3-치환 티오펜) (poly(3-substituted thiophene)), 폴리(3,4-이치환 티오펜) (poly(3,4-bisubstituted thiophene)), 폴리벤조티오펜 (polybenzothiophene)), 폴리이소티아 나프텐 (polyisothianaphthene), 폴리(N-치환 피롤) (poly(N-substituted pyrrole)), 폴리(3-치환 피롤) (poly(3-substituted pyrrole)), 폴리(3,4-이치환 피롤) (poly(3,4-bisubstituted pyrrole)), 폴리퓨란(polyfuran), 폴리피리딘(polypyridine), 폴리-1,3,4-옥사디아졸 (poly-1,3,4-oxadiazoles), 폴리이소티아나프텐(polyisothianaphthene), 폴리(N-치환 아닐린) (poly(N-substituted aniline)), 폴리(2-치환 아닐린) (poly(2-substituted aniline)), 폴리(3-치환 아닐린) (poly(3-substituted aniline)), 폴리(2,3-치환 아닐린) (poly(2,3-bisubstituted aniline)), 폴리아줄렌 (polyazulene), 폴리피렌 (polypyrene)과 같은 공액 헤테로고리형 폴리머; 피라졸린 화합물 (pyrazoline compounds); 폴리셀레노펜 (polyselenophene); 폴리벤조퓨란 (polybenzofuran); 폴리인돌 (polyindole); 폴리피리다진 (polypyridazine); 벤지딘 화합물 (benzidine compounds); 스틸벤 화합물 (stilbene compounds); 트리아진 (triazines); 치환된 메탈로- 또는 메탈-프리 포르핀 (substituted metallo- or metal-free porphines), 프탈로시아닌 (phthalocyanines), 플루오로프탈로시아닌 (fluorophthalocyanines), 나프탈로시아닌 (naphthalocyanines) 또는 플루오로나프탈로시아닌 (fluoronaphthalocyanines); C60 및 C70 풀러렌(fullerenes); N,N'-디알킬, 치환된 디알킬, 디아릴 또는 치환된 디아릴-1,4,5,8-나프탈렌테트라카르복실릭 디이미드 (N,N'-dialkyl, substituted dialkyl, diaryl or substituted diaryl-1,4,5,8-naphthalenetetracarboxylic diimide) 및 불화 유도체; N,N'-디알킬, 치환된 디알킬, 디아릴 또는 치환된 디아 릴 3,4,9,10-페릴렌테트라카르복실릭 디이미드 (N,N'-dialkyl, substituted dialkyl, diaryl or substituted diaryl 3,4,9,10-perylenetetracarboxylic diimide); 배쏘페난쓰롤린 (bathophenanthroline); 디페노퀴논 (diphenoquinones); 1,3,4-옥사디아졸 (1,3,4-oxadiazoles); 11,11,12,12-테트라시아노나프토-2,6-퀴노디메탄 (11,11,12,12-tetracyanonaptho-2,6-quinodimethane); α,α'-비스(디티에노[3,2-b2',3'-d]티오펜) (α,α'-bis(dithieno[3,2-b2',3'-d]thiophene)); 2,8-디알킬, 치환된 디알킬, 디아릴 또는 치환된 디아릴 안트라디티오펜 (2,8-dialkyl, substituted dialkyl, diaryl or substituted diaryl anthradithiophene); 2,2'-비벤조[1,2-b:4,5-b']디티오펜 (2,2'-bibenzo[1,2-b:4,5-b']dithiophene) 등의 유기 반-전도성(semi-conducting) 재료나 이들의 화합물, 올리고머 및 화합물 유도체 등이 사용될 수 있다.And other conjugated hydrocarbon polymers such as polyacene, polyphenylene, poly (phenylene vinylene), polyfluorene, and oligomers of such conjugated hydrocarbons. ; Condensed aromatic hydrocarbons such as anthracene, tetratracene, chrysene, pentacene, pyrene, perylene and coronene; oligomeric para substitutions such as p-quaterphenyl (p-4P), p-quinquephenyl (p-5P), p-sexiphenyl (p-6P) Oligomeric para substituted phenylenes; Poly (3-substituted thiophene), poly (3,4-bisubstituted thiophene), polybenzothiophene, poly Isotia naphthene (polyisothianaphthene), poly (N-substituted pyrrole), poly (3-substituted pyrrole), poly (3,4-disubstituted pyrrole) ) (poly (3,4-bisubstituted pyrrole)), polyfuran, polypyridine, poly-1,3,4-oxadiazoles, polyiso Polyisothianaphthene, poly (N-substituted aniline), poly (2-substituted aniline), poly (2-substituted aniline), poly (3-substituted aniline) (poly Conjugated heterocyclic polymers such as (3-substituted aniline), poly (2,3-bisubstituted aniline), polyazulene, polypyrene; Pyrazoline compounds; Polyselenophene; Polybenzofuran; Polyindole; Polypyridazine; Benzidine compounds; Stilbene compounds; Triazines; Substituted metallo- or metal-free porphines, phthalocyanines, fluorophthalocyanines, naphthalocyanines or fluoronaphthalocyanines; C 60 and C 70 fullerenes; N, N'-dialkyl, substituted dialkyl, diaryl or substituted diaryl-1,4,5,8-naphthalenetetracarboxylic diimide (N, N'-dialkyl, substituted dialkyl, diaryl or substituted diaryl-1,4,5,8-naphthalenetetracarboxylic diimide) and fluorinated derivatives; N, N'-dialkyl, substituted dialkyl, diaryl or substituted diaryl 3,4,9,10-perylenetetracarboxylic diimide (N, N'-dialkyl, substituted dialkyl, diaryl or substituted diaryl 3,4,9,10-perylenetetracarboxylic diimide); Bathophenanthroline; Diphenoquinones; 1,3,4-oxadiazoles (1,3,4-oxadiazoles); 11,11,12,12-tetracyanonaphtho-2,6-quinodimethane (11,11,12,12-tetracyanonaptho-2,6-quinodimethane); α, α'-bis (dithieno [3,2-b2 ', 3'-d] thiophene) (α, α'-bis (dithieno [3,2-b2', 3'-d] thiophene) ); 2,8-dialkyl, substituted dialkyl, diaryl or substituted diaryl anthrathiothiophenes (2,8-dialkyl, substituted dialkyl, diaryl or substituted diaryl anthradithiophene); Organic groups such as 2,2'-bibenzo [1,2-b: 4,5-b '] dithiophene (2,2'-bibenzo [1,2-b: 4,5-b'] dithiophene) Semi-conducting materials or their compounds, oligomers and compound derivatives can be used.

BFO에 대한 유기물의 혼합비는 필요에 따라 적절하게 설정하는 것이 가능하다. 만일 유기물의 혼합비가 높아지게 되면 혼합물의 다강특성은 낮아지는 반면에 형성온도와 누설전류값은 낮아지게 되고, 유기물의 혼합비가 낮아지게 되면 혼합물의 다강특성은 높아지는 반면에 형성온도와 누설전류값은 높아지게 된다.The mixing ratio of organic matter to BFO can be appropriately set as necessary. If the mixing ratio of the organic material is increased, the multi-temperature characteristics of the mixture are lowered while the formation temperature and leakage current value are lowered. If the mixing ratio of organic materials is lowered, the multi-temperature property of the mixture is increased while the formation temperature and leakage current value are increased. do.

한편, BFO와 유기물의 혼합물은 예컨대 다음 방식을 통해 형성할 수 있다.On the other hand, a mixture of BFO and organics can be formed, for example, in the following manner.

1. BFO와 유기물(또는 유기물 다강체) 파우더를 혼합한 후, 이를 용매에 녹여서 혼합 용액을 생성.1. After mixing BFO and organic (or organic multi-rigid) powder, dissolve it in a solvent to produce a mixed solution.

2. BFO 용액에 유기물(또는 유기물 다강체) 파우더를 용해시켜 혼합 용액을 생성.2. Dissolve the organic (or organic multi-rigid) powder in the BFO solution to form a mixed solution.

3. 유기물(또는 유기물 다강체) 용액에 BFO 파우더를 용해시켜 혼합 용액을 생성.3. Dissolve the BFO powder in an organic (or organic multi-rigid) solution to form a mixed solution.

4. BFO 용액과 유기물(또는 유기물 다강체) 용액을 혼합하여 혼합 용액을 생성.4. Mix the BFO solution and the organic (or organic multi-rigid) solution to form a mixed solution.

본 발명에 따른 다강체 물질은 다음과 같은 특성을 갖는다.The multi-rigid material according to the invention has the following characteristics.

1. BFO와 유기물의 혼합 용액을 이용하여 다강체층을 형성하게 되므로, 잉크젯, 스핀코팅법 또는 스크린 인쇄 등을 이용하여 용이하게 다강체층을 형성할 수 있게 된다.1. Since a multi-rigid layer is formed using a mixed solution of BFO and organic matter, it is possible to easily form a multi-rigid layer using inkjet, spin coating, or screen printing.

2. 다강체층의 형성온도가 낮아지게 되므로 실리콘 기판상에 고품질의 다강체층을 형성할 수 있게 된다.2. Since the formation temperature of the multi-rigid layer is lowered, it is possible to form a high-quality multi-rigid layer on the silicon substrate.

3. 다강체층의 형성온도가 낮아지게 되므로 압전소자, 초전소자, 전계효과 트랜지스터, 강유전체 메모리를 기존의 실리콘 기판 대신에 유기물이나 종이 등과 같은 다양한 종류의 기판 상에 형성할 수 있게 된다.3. As the formation temperature of the multi-rigid layer is lowered, piezoelectric elements, pyroelectric elements, field effect transistors, and ferroelectric memories can be formed on various kinds of substrates such as organic materials or paper instead of the conventional silicon substrates.

4. 다강체층의 유전율이 매우 높으면서 그 누설전류값이 대폭 낮아지게 되므로 데이터 저장 능력이 우수한 캐패시터를 구현할 수 있게 된다. 4. Since the dielectric constant of the multi-rigid layer is very high and the leakage current value is significantly lowered, it is possible to implement a capacitor having excellent data storage capability.

본 발명에 따른 다강체 물질은 그 형성 온도가 낮기 때문에 기판으로서 기존의 Si, Ge 웨이퍼를 비롯하여, 종이, 파릴렌(Parylene) 등의 코딩재가 도포된 종이, 또는 유연성을 갖는 플라스틱 등의 유기물을 이용할 수 있다. 또한, 이때 이용가능한 유기물로서는 폴리이미드(PI), 폴리카보네이트(PC), 폴리에테르설폰(PES), 폴리에테르에테르케톤(PEEK), 폴리부틸렌테레프탈레이트(PBT), 폴리에틸렌테레프탈 레이트(PET), 폴리염화비닐(PVC), 폴리에틸렌(PE), 에틸렌 공중합체, 폴리프로필렌(PP), 프로필렌 공중합체, 폴리(4-메틸-1-펜텐)(TPX), 폴리아릴레이트(PAR), 폴리아세탈(POM), 폴리페닐렌옥사이드(PPO), 폴리설폰(PSF), 폴리페닐렌설파이드(PPS), 폴리염화비닐리덴(PVDC), 폴리초산비닐(PVAC), 폴리비닐알콜(PVAL), 폴리비닐아세탈, 폴리스티렌(PS), AS수지, ABS수지, 폴리메틸메타크릴레이트(PMMA), 불소수지, 페놀수지(PF), 멜라민수지(MF), 우레아수지(UF), 불포화폴리에스테르(UP), 에폭시수지(EP), 디알릴프탈레이트수지(DAP), 폴리우레탄(PUR), 폴리아미드(PA), 실리콘수지(SI) 또는 이것들의 혼합물 및 화합물을 이용할 수 있다.Since the multi-rigid material according to the present invention has a low formation temperature, it is possible to use organic materials such as conventional Si, Ge wafers, papers coated with paper, parylene, or the like, or flexible plastics, as substrates. Can be. In addition, the organic materials usable here include polyimide (PI), polycarbonate (PC), polyether sulfone (PES), polyether ether ketone (PEEK), polybutylene terephthalate (PBT), polyethylene terephthalate (PET), Polyvinyl chloride (PVC), polyethylene (PE), ethylene copolymer, polypropylene (PP), propylene copolymer, poly (4-methyl-1-pentene) (TPX), polyarylate (PAR), polyacetal ( POM), polyphenylene oxide (PPO), polysulfone (PSF), polyphenylene sulfide (PPS), polyvinylidene chloride (PVDC), polyvinyl acetate (PVAC), polyvinyl alcohol (PVAL), polyvinyl acetal , Polystyrene (PS), AS resin, ABS resin, polymethyl methacrylate (PMMA), fluorine resin, phenol resin (PF), melamine resin (MF), urea resin (UF), unsaturated polyester (UP), epoxy Resin (EP), diallyl phthalate resin (DAP), polyurethane (PUR), polyamide (PA), silicone resin (SI) or mixtures and combinations thereof The can be used.

상기한 바와 같이 BFO는 그 형성온도가 높기 때문에 이를 실리콘 기판상에 형성할 때 여러가지 문제가 발생하게 된다. 이에 반하여, 본 발명에 따른 BFO 혼합물은 예컨대 200도 이하의 저온에서 형성할 수 있게 된다.As described above, since the BFO has a high forming temperature, various problems occur when the BFO is formed on a silicon substrate. In contrast, the BFO mixtures according to the invention can be formed, for example, at low temperatures below 200 degrees.

또한, 다강체층을 잉크젯, 스핀코팅법 또는 스크린 인쇄 등을 이용하여 형성할 수 있게 되고 BFO 합성물질의 누설전류값이 대폭 낮아지게 되므로, 다강체층을 예컨대 1㎛ 이하의 두께로 형성할 수 있게 된다. 다강체층의 두께가 얇아지게 되면 다강체에 대한 인가전압을 매우 낮출 수 있게 된다. 이는 본 발명에 따른 BFO 합성 물질을 이용하게 되면 매우 저전압에서 동작할 수 있는 전자 및 전기 소자를 제작할 수 있다는 것을 의미한다.In addition, since the multi-rigid layer can be formed by inkjet, spin coating, or screen printing, and the leakage current value of the BFO composite material is significantly lowered, the multi-rigid layer can be formed with a thickness of, for example, 1 μm or less. Will be. When the thickness of the multi-rigid layer becomes thin, the applied voltage to the multi-rigid body can be very low. This means that by using the BFO composite material according to the present invention it is possible to manufacture electronic and electrical devices that can operate at very low voltage.

이상으로 본 발명에 따른 실시예를 설명하였다. 그러나, 본 발명은 상기한 실시예에 한정되지 않고 그 기술적 사상을 벗어나지 않는 범위내에서 다양하게 변형시켜 실시할 수 있다.The embodiment according to the present invention has been described above. However, the present invention is not limited to the above-described embodiments and can be carried out in various modifications without departing from the spirit thereof.

Claims (16)

BFO에 대하여 유기물을 혼합하여 구성되는 것을 특징으로 하는 BFO를 주성분으로 하는 강유전 물질.A ferroelectric material containing BFO as a main component, characterized by mixing organic matter with respect to BFO. 제1항에 있어서,The method of claim 1, 상기 유기물이 유기물 다강체인 것을 특징으로 하는 BFO를 주성분으로 하는 강유전 물질.A ferroelectric material containing BFO as a main component, wherein the organic material is an organic material multi-rigid body. 제2항에 있어서,The method of claim 2, 상기 유기물 다강체는 폴리비닐리덴 플로라이드(PVDF)와, PVDF를 포함하는 중합체, 공중합체 또는 삼원공중합체, 시아노중합체 및 이들의 중합체나 공중합체 중 하나인 것을 특징으로 하는 BFO를 주성분으로 하는 강유전 물질.The organic multi-rigid body is a polyvinylidene fluoride (PVDF), and a polymer, copolymer or terpolymer, PVFO containing cydamide, cyano polymer and one of these polymers or copolymers, characterized in that the BFO as a main component Ferroelectric materials. 제2항에 있어서,The method of claim 2, 상기 유기물 다강체는 PVDF-TRFE인 것을 특징으로 하는 BFO를 주성분으로 하는 강유전 물질.The organic multi-rigid body is a ferroelectric material based on BFO, characterized in that PVDF-TRFE. 제1항에 있어서,The method of claim 1, 상기 BFO와 유기물의 혼합물이 용액상태인 것을 특징으로 하는 BFO를 주성분 으로 하는 강유전 물질.Ferroelectric material based on the BFO, characterized in that the mixture of the BFO and the organic material in a solution state. 제5항에 있어서,The method of claim 5, 상기 혼합용액은 BFO와 유기물 파우더를 혼합한 후, 이를 용매에 녹여서 생성하는 것을 특징으로 하는 BFO를 주성분으로 하는 강유전 물질.The mixed solution is a ferroelectric material containing BFO as a main component, which is produced by mixing BFO and organic powder, and then dissolving it in a solvent. 제5항에 있어서,The method of claim 5, 상기 혼합용액이 BFO 용액에 유기물 파우더를 용해시켜 생성되는 것을 특징으로 하는 BFO를 주성분으로 하는 강유전 물질.Ferroelectric material based on the BFO, characterized in that the mixed solution is produced by dissolving the organic powder in the BFO solution. 제5항에 있어서,The method of claim 5, 상기 혼합용액이 유기물 용액에 BFO 파우더를 용해시켜 생성되는 것을 특징으로 하는 BFO를 주성분으로 하는 강유전 물질.A ferroelectric material containing BFO as a main component, wherein the mixed solution is produced by dissolving BFO powder in an organic solution. 제5항에 있어서,The method of claim 5, 상기 혼합용액이 BFO 용액과 유기물 용액을 혼합하여 생성되는 것을 특징으로 하는 BFO를 주성분으로 하는 강유전 물질.Ferroelectric material based on the BFO, characterized in that the mixed solution is produced by mixing the BFO solution and the organic solution. 다강체층을 제조하는 방법에 있어서,In the method for producing a multi-rigid layer, BFO와 유기물의 혼합용액을 생성하는 단계와,Generating a mixed solution of BFO and organic matter, 상기 혼합용액을 이용하여 기판상에 다강체층을 형성하는 단계 및,Forming a multi-rigid layer on the substrate using the mixed solution; 상기 다강체층을 소성하는 단계를 포함하여 구성되는 것을 특징으로 하는 다강체층 제조방법.Method for producing a multi-rigid layer characterized in that it comprises a step of firing the multi-rigid layer. 제10항에 있어서,The method of claim 10, 상기 혼합용액은 BFO와 유기물 파우더를 혼합한 후, 이를 용매에 녹여서 생성하는 것을 특징으로 하는 다강체층 제조방법.The mixed solution is a multi-body layer manufacturing method characterized in that after mixing the BFO and the organic powder, it is dissolved in a solvent to produce. 제10항에 있어서,The method of claim 10, 상기 혼합용액이 BFO 용액에 유기물 파우더를 용해시켜 생성되는 것을 특징으로 하는 다강체층 제조방법.The mixed solution is produced by dissolving the organic powder in the BFO solution multi-layer layer production method. 제10항에 있어서,The method of claim 10, 상기 혼합용액이 유기물 용액에 BFO 파우더를 용해시켜 생성되는 것을 특징으로 하는 다강체층 제조방법.Method for producing a multi-rigid layer characterized in that the mixed solution is produced by dissolving BFO powder in an organic solution. 제10항에 있어서,The method of claim 10, 상기 혼합용액이 BFO 용액과 유기물 용액을 혼합하여 생성되는 것을 특징으로 하는 다강체층 제조방법.The mixed solution is a multi-rigid layer manufacturing method characterized in that the produced by mixing the BFO solution and the organic solution. 제10항에 있어서,The method of claim 10, 상기 다강체층의 형성은 잉크젯, 스핀코팅법 또는 스크린 인쇄 중 하나를 이용하여 실행되는 것을 특징으로 하는 다강체층 제조방법.Forming the multi-rigid layer is a method for producing a multi-rigid layer, characterized in that carried out using one of the inkjet, spin coating method or screen printing. 제10항에 있어서,The method of claim 10, 상기 기판은 종이, 코딩재가 도포된 종이, 유연성을 갖는 플라스틱 중 적어도 하나를 포함하여 구성되는 것을 특징으로 하는 다강체층 제조방법.The substrate is a method of manufacturing a multi-rigid layer characterized in that it comprises at least one of paper, paper coated with a coding material, plastic having flexibility.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101122631B1 (en) * 2010-09-17 2012-03-09 한국기계연구원 Complex perovskite ceramics and films with superior room temperature multiferroic properties, and the fabrication method thereof
CN106893236A (en) * 2017-03-01 2017-06-27 东北大学秦皇岛分校 A kind of bismuth ferrite composite organic-inorganic material and preparation method thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101122631B1 (en) * 2010-09-17 2012-03-09 한국기계연구원 Complex perovskite ceramics and films with superior room temperature multiferroic properties, and the fabrication method thereof
CN106893236A (en) * 2017-03-01 2017-06-27 东北大学秦皇岛分校 A kind of bismuth ferrite composite organic-inorganic material and preparation method thereof

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