WO2014196776A1 - Procédé de transfert et d'adhérence de nano-couche mince - Google Patents

Procédé de transfert et d'adhérence de nano-couche mince Download PDF

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Publication number
WO2014196776A1
WO2014196776A1 PCT/KR2014/004904 KR2014004904W WO2014196776A1 WO 2014196776 A1 WO2014196776 A1 WO 2014196776A1 KR 2014004904 W KR2014004904 W KR 2014004904W WO 2014196776 A1 WO2014196776 A1 WO 2014196776A1
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WIPO (PCT)
Prior art keywords
substrate
thin film
conductive plate
adhesive
adhesive substrate
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Ceased
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PCT/KR2014/004904
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English (en)
Korean (ko)
Inventor
한창수
정원석
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Korea University Research and Business Foundation
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Korea University Research and Business Foundation
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P90/00—Preparation of wafers not covered by a single main group of this subclass, e.g. wafer reinforcement
    • H10P90/19—Preparing inhomogeneous wafers
    • H10P90/1904—Preparing vertically inhomogeneous wafers
    • H10P90/1906—Preparing SOI wafers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P95/00—Generic processes or apparatus for manufacture or treatments not covered by the other groups of this subclass
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P14/00—Formation of materials, e.g. in the shape of layers or pillars
    • H10P14/20—Formation of materials, e.g. in the shape of layers or pillars of semiconductor materials
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
    • H10W10/00—Isolation regions in semiconductor bodies between components of integrated devices
    • H10W10/10—Isolation regions comprising dielectric materials
    • H10W10/181—Semiconductor-on-insulator [SOI] isolation regions, e.g. buried oxide regions of SOI wafers

Definitions

  • the present invention relates to a method of transferring and bonding a thin film having a thickness of 2 ⁇ m or less to various substrates, and more particularly, to detach and bond a thin film and a substrate using an electric field while applying pressure, and to manufacture the above-described structure.
  • By implementing the device it is possible to adjust the temperature and the surrounding gas environment to improve adhesion.
  • the technology of easily detaching and transferring nano thin films and attaching them to strongly desired substrates can be useful for a variety of applications.
  • the substrate is removed or glued off for stronger bonding.
  • a physical (thermal or mechanical crimping) method is used for bonding.
  • these conventional methods have difficulty in utilizing unique material properties because they may occur when a part of the material needs to be damaged or added.
  • the adhesion to the target substrate is not great when the chemical thin film is attached through a chemical treatment or a simple van der Waals force, which causes problems in manufacturing devices or components in the future.
  • the conventional graphene because it is transferred to the substrate using an intermediate material such as PMMA, due to the residual PMMA residue (residue), there was an element that is inherent in graphene characteristics.
  • the present invention seeks to develop a method for removing a nanothick thin film from an original grown substrate or attaching it firmly to a desired substrate.
  • the present invention for achieving the above object is characterized in that the pressing force and the electric field at the same time to attach the nano-thin material having a two-dimensional form and having a thickness of less than ⁇ m to the substrate.
  • the graphene nano thin film is placed on a conventional SiO 2 / Si substrate, and a voltage is applied while pressing a conductive plate capable of applying voltage at both ends.
  • the application of such a voltage allows the nano thin film to be attached very uniformly on the substrate, and may also contribute to improving the bonding strength between materials depending on the material in the nano thin film.
  • the adhesion between the target substrate and the nano thin film is made well, it is possible to increase the mutual bonding force.
  • the present invention not only provides a very high adhesion and adhesion by itself as the nano thin film material makes uniform contact with the target substrate, but also when the nano material is composed of a network of a plurality of independent nano materials. It can contribute to improving the bonds between the materials that make up these networks. In other words, heat or magnetic force may be generated only in the nanomaterials by an electric field applied to the nanomaterials, which may help to improve the bonding force between the materials.
  • the substrate with the improved adhesion of the nano thin film not only improves the performance of the device, but also exhibits excellent properties such as delamination prevention, anti-vapor permeation, and the stability and reliability of the device or component. Can improve.
  • Example 1 is a schematic view of the bonding process according to Example 1.
  • One aspect of the present invention comprises the steps of (a) contacting one surface of the adhesive substrate and one surface of the thin film, (b) applying pressure to the other surface of the adhesive substrate and the other surface of the thin film to compress the adhesive substrate and the thin film, (C) a method for bonding the substrate and the thin film comprising the step of applying an electric field to the other surface of the adhesive substrate and the other surface of the thin film.
  • step (b) and step (c) may be performed at the same time, 2 step (c) may be performed in a state in which pressure is applied according to step (b), or 3 step (c) Accordingly, step (b) may be performed in a state where an electric field is applied.
  • step (a) means that the thin film grown on another substrate is transferred to the adhesive substrate by conventional methods such as wet transfer or dry transfer to contact the thin film and the substrate.
  • the step (c) is to contact the first planar conductive plate and the second planar conductive plate 1 contact the adhesive substrate and the thin film, respectively, or 2 contact the adhesive substrate and the thin film growth substrate, respectively And applying voltage to the first planar conductive plate and the second planar conductive plate.
  • the two planar conductive plates may be made of the same material or different materials.
  • only the Cu electrode itself may be used as each of the conductive plates, or a Ni plate and a Cu electrode may be used together.
  • the substrate may be a conductor.
  • examples of the glass-based material include, but are not limited to, Pyrex, Boroflat 33, and the like;
  • Examples of the metal oxide include, but are not limited to, SiO 2 , Al 2 O 3 , NiO, and the like;
  • Examples of the semiconductor insulator include, but are not limited to, SiO 2 , HfO, SiN, Al 2 O 3 , SiC, and the like;
  • Examples of the polymer include but are not limited to polyethylene terephthalate (PET), polycarbonate (PC), polystyrene (PS), polydimethylsiloxane (PDMS) and the like.
  • the adhesive substrate may be a substrate composed of one or more materials selected from glass-based materials, polymers, metals, metal oxides, semiconductors, and semiconductor insulators.
  • the thin film growth substrate may be a substrate made of one or more materials selected from metals, semiconductors, and semiconductor insulators.
  • the thin film is 1 graphene, graphene oxide, h-BN, MoS x , WS x , two-dimensional thin film selected from a combination of two or more thereof;
  • a two-dimensional thin film composed of carbon nanotubes or a two-dimensional thin film composed of nanowires; 3 may be at least one selected from the complex thin films in which nanoparticles are bonded to the two-dimensional thin film or the two-dimensional thin film.
  • a two-dimensional thin film may be a single layer thin film or a multi-layer thin film
  • a single layer is more preferable for the application of the present invention.
  • x used in MoS x and WS x means a positive number, such a notation can be seen in European Patent Publication Nos. 2554151 and 2520547, US Patent Publication No. 2012/0244411, and the like. It is a notation widely used and easily understood in the technical field to which the present invention belongs.
  • the nanowires include, but are not limited to, Si, ZnO, TiO 2 , SnO 2 , and the like;
  • the nanoparticles include, but are not limited to Au, Ag, Ti, CdS and the like.
  • very thin and flexible materials such as monolayer graphene, are generally preferred, but may also be used for other thin films of semiconductors, insulators, and conductors having a thickness of 1 ⁇ m or less.
  • the bonding substrate is a SiO 2 / Si substrate having a SiO 2 layer on the surface of the Si substrate;
  • the thin film is graphene;
  • the thin film growth substrate is a Cu substrate; Transcription is performed by a wet transcription mode;
  • the first conductive plate is a Cu electrode;
  • the second conductive plate is a double-layered plate of a nickel plate and a Cu electrode, and the nickel plate is positioned on the side in contact with the thin film;
  • the voltage may be equal to or less than the dielectric breakdown voltage of SiO 2.
  • the transcription is performed by a wet transcription method;
  • the first planar conductive plate and the second planar conductive plate are in contact with the adhesive substrate and the thin film, respectively, or 2 the contact with the adhesive substrate and the thin film growth substrate, respectively, and the first plane
  • the adhesive substrate is selected from SiO 2 / Si substrate, (ii) a polymer substrate, (iii) an organic substrate formed of a SiO 2 layer on the surface of the Si substrate (i);
  • the thin film is graphene;
  • the thin film growth substrate is a Cu substrate;
  • the first conductive plate is a Cu electrode;
  • the second conductive plate is a bilayer plate of a Cu electrode and a flat plate; One of the Cu electrode and the plate is in contact with the thin film;
  • the voltage is less than or equal to the dielectric breakdown voltage of SiO 2 ;
  • the flat plate is a metal which is hard to ionize by an electric field at high temperature, particularly a metal which is hard to ionize by an electric field at high temperature, and is typically a substrate of a metal such as nickel.
  • a method of contacting a thin film grown on at least one surface of (a '') one surface of an adhesive substrate with both surfaces of the thin film growth substrate Applying pressure to the other surface of the adhesive substrate and the other surface of the both sides of the thin film growth substrate opposite to the surface on which the thin film compressed to the adhesive substrate is grown, (c '') the other surface of the adhesive substrate and the thin film growth substrate. It relates to a substrate and a thin film bonding method comprising the step of applying an electric field to the other surface.
  • the step (b '') and the step (c '') may be carried out at the same time, 2
  • the step (c '') may be performed in the state that the pressure is applied according to the step (b ''), , Or 3
  • the step (b '') may be performed in a state where an electric field is applied according to the step (c '').
  • the thin film may have a thickness of 0.3 nm to 1 ⁇ m.
  • the side surface relates to a bonding method or a transfer method that can be directly transferred to the adhesive substrate without detaching the thin film grown on the other substrate.
  • the step (c '') may include contacting the first planar conductive plate and the second planar conductive plate to the adhesive substrate and the thin film, respectively, or 2 to the adhesive substrate and the thin film growth substrate. And the voltage is applied to the first planar conductive plate and the second planar conductive plate, respectively.
  • the two planar conductive plates may be made of the same material or different materials.
  • the substrate is a conductor.
  • step (c '') may be performed by placing a nonconductor between the two planar conductive plates and applying a voltage below the dielectric breakdown voltage of the nonconductor to the two planar conductive plates.
  • the thin film growth substrate may be a substrate made of one or more materials selected from metals, semiconductors, and semiconductor insulators.
  • the thin film is 1 graphene, graphene oxide, h-BN, MoS x , WS x , two-dimensional thin film selected from a combination of two or more thereof;
  • a two-dimensional thin film composed of carbon nanotubes or a two-dimensional thin film composed of nanowires; 3 may be at least one selected from the complex thin films in which nanoparticles are bonded to the two-dimensional thin film or the two-dimensional thin film.
  • the at least one step selected from the contacting, applying the pressure and applying the electric field may be performed under additional conditions besides the electric field and pressure.
  • the conductive plate may be surface treated to prevent adhesion.
  • the adhesive substrate is a polymer;
  • the thin film is graphene;
  • the thin film growth substrate is a Cu substrate;
  • the first conductive plate is a Cu electrode;
  • the second conductive plate may be a double layer plate of a nickel plate and a Cu electrode, and the nickel plate may be positioned to contact the thin film growth substrate.
  • the step (c '') may include contacting the first planar conductive plate and the second planar conductive plate to the adhesive substrate and the thin film, respectively, or the adhesive substrate and the thin film growth substrate. Contacting each other, and applying a voltage to the first planar conductive plate and the second planar conductive plate;
  • the adhesive substrate is selected from SiO 2 / Si substrate, (ii) a polymer substrate, (iii) a glass substrate having a SiO 2 layer on the surface of the Si substrate (i);
  • the thin film is graphene;
  • the thin film growth substrate is a Cu substrate;
  • the first conductive plate is a Cu electrode;
  • the second conductive plate is a bilayer plate of a Cu electrode and a flat plate; One of the Cu electrode and the plate is in contact with the thin film;
  • the adhesive substrate is the SiO 2 / Si substrate, the voltage is equal to or less than the dielectric breakdown voltage of SiO 2 ;
  • the adhesive substrate is the polymer substrate, at least one of the
  • the flat plate is a metal which is hard to ionize by an electric field at high temperature, particularly a metal which is hard to ionize by an electric field at high temperature, and is typically a substrate of a metal such as nickel.
  • the present invention relates to a method of attaching a nano thin film made of nanomaterials in a two-dimensional form by applying a physical crimping and an electric field in order to attach to a desired substrate. Can be performed.
  • Two-dimensional nanomaterials according to the present invention typically include graphene, graphene oxide, and two-dimensional forms of materials such as h-BN, MoS x , WS x, and a hybrid structure thereof.
  • Fin-hBN and the one-dimensional wire form, such as carbon nanotubes, nanowires (Si, ZnO, TiO 2 , SnO 2, etc.) in the form of a film in the form of a two-dimensional film or the one-dimensional Or nano thin films made of a combined material of a two-dimensional material and a zero-dimensional material (various nanoparticles; for example, Au, Ag, Ti, CdS, etc.).
  • very thin and flexible materials such as monolayer graphene are preferred, but may also be used for other thin films of semiconductors, insulators, and conductors having a thickness of less than 1 ⁇ m.
  • the bonding method of the present invention it is essential to apply an electric field and a compressive force, but in addition thereto, a specific gas, a vacuum, a temperature change, etc. may be additionally added. In particular, it is desirable to apply the applied voltage below the dielectric breakdown voltage of the insulator used in the bonding process.
  • the substrate when the substrate is an insulator, a nano thin film is placed on the insulator without using a separate insulator, and the nano thin film and the insulator substrate can be attached by pressing and applying an electric field.
  • a material or a polymer PET, polycarbonate, PDMS, polystyrene, etc.
  • an insulator of a semiconductor device such as glass, SiO 2 HfO, SiN, and Al 2 O 3 .
  • the nano thin film adheres well to the substrate and, conversely, the surface of the conductive plate (hydrophilic, hydrophobic, sel-assembly monolayer, etc.) is reduced so that it sticks well to the conductive plate to which voltage is applied. You can.
  • the bonding force between the substrate and the nano thin film is so strong that it is very difficult to directly transfer and attach to the desired substrate. Therefore, conventionally, the substrate on which the nano thin film is grown is chemically removed first, and then the nano thin film is transferred. At this time, a number of problems occur, and using the method of the present invention, the nano thin film grown on the substrate can be directly transferred and attached by applying an electric field and a mechanical compressive force simultaneously without this process. For example, graphene grown on a metal substrate such as Cu or Ni can be directly transferred onto the polymer substrate by the method of the present invention without any other process, and can be attached very strongly.
  • the substrate used may include not only a metal substrate such as Cu and Ni, but also an insulator such as a semiconductor or SiC, and the thickness of graphene, carbon nanotubes, nanowires and ⁇ m or less described above as a nano thin film.
  • a thin film may be used.
  • the basic example may be represented as shown in FIG. 1.
  • the graph in red is a characteristic of graphene before bonding, and it can be seen that the intensity ratio of 2D (2670 cm ⁇ 1 band) / G peak (1590 cm ⁇ 1 band) representing a single layer remains the same.
  • the peak value of the 1350 cm -1 band to determine the damage factor of the graphene is observed to be very small before and after the bonding, it can be seen that the electrical properties of the graphene is well maintained after the bonding.
  • Cu is grown on a Cupper film by chemical vapor deposition (CVD), followed by Cu by wet transfer or dry transfer. After etching, the process of transferring to a substrate such as PET.
  • CVD chemical vapor deposition

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  • Carbon And Carbon Compounds (AREA)
  • Laminated Bodies (AREA)
  • Thin Film Transistor (AREA)

Abstract

La présente invention concerne un procédé permettant de faire fortement adhérer une nano-couche mince bidimensionnelle sur un substrat souhaité et, plus particulièrement, un procédé par lequel l'adhésivité d'une couche extrêmement mince présentant une nano-épaisseur, tel que du graphène, du MoS2, du WS, du h-BN, une couche mince à nanotube de carbone et une couche mince à nanofil, sur un substrat, est augmentée au moyen d'une pression mécanique et au moyen d'un champ électrique, et par lequel du graphène en croissance sur un substrat en Cu est transféré directement et collé sans médiateur sur un substrat polymère tel que du PET, au moins un côté présentant un isolant.
PCT/KR2014/004904 2013-06-04 2014-06-03 Procédé de transfert et d'adhérence de nano-couche mince Ceased WO2014196776A1 (fr)

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KR10-2013-0063821 2013-06-04
KR1020130063821A KR101505471B1 (ko) 2013-06-04 2013-06-04 나노박막의 전사 및 접착방법

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Cited By (3)

* Cited by examiner, † Cited by third party
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CN109879277A (zh) * 2019-04-16 2019-06-14 电子科技大学 一种石墨烯清洁转移方法
CN110436449A (zh) * 2019-09-11 2019-11-12 西安交通大学 一种基于电辅助液桥的二维材料转移方法
CN114730696A (zh) * 2019-11-15 2022-07-08 明尼苏达大学董事会 用于石墨烯制造工艺的转移材料层

Families Citing this family (3)

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KR101732943B1 (ko) 2015-06-25 2017-05-24 한국과학기술연구원 이차원 전이금속 디칼코겐 화합물을 발광층으로 하는 발광소자와 그 제조방법
KR20170018718A (ko) 2015-08-10 2017-02-20 삼성전자주식회사 비정질 합금을 이용한 투명 전극 및 그 제조 방법
KR101723769B1 (ko) * 2016-02-17 2017-04-05 원광대학교산학협력단 그래핀의 직접 전사 방법 및 그래핀층 상의 선택적 원자층 증착 방법

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Publication number Priority date Publication date Assignee Title
CN109879277A (zh) * 2019-04-16 2019-06-14 电子科技大学 一种石墨烯清洁转移方法
CN110436449A (zh) * 2019-09-11 2019-11-12 西安交通大学 一种基于电辅助液桥的二维材料转移方法
CN110436449B (zh) * 2019-09-11 2020-11-17 西安交通大学 一种基于电辅助液桥的二维材料转移方法
CN114730696A (zh) * 2019-11-15 2022-07-08 明尼苏达大学董事会 用于石墨烯制造工艺的转移材料层

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