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WO2023075201A1 - Électronique extensible de type à couche mince comprenant un substrat extensible et son procédé de fabrication - Google Patents

Électronique extensible de type à couche mince comprenant un substrat extensible et son procédé de fabrication Download PDF

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Publication number
WO2023075201A1
WO2023075201A1 PCT/KR2022/015255 KR2022015255W WO2023075201A1 WO 2023075201 A1 WO2023075201 A1 WO 2023075201A1 KR 2022015255 W KR2022015255 W KR 2022015255W WO 2023075201 A1 WO2023075201 A1 WO 2023075201A1
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substrate
stretchable
thin
electronic device
treated
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이정용
전연지
이승복
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Korea Advanced Institute of Science and Technology KAIST
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • C08L9/06—Copolymers with styrene
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F71/00—Manufacture or treatment of devices covered by this subclass
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F77/00—Constructional details of devices covered by this subclass
    • H10F77/10—Semiconductor bodies
    • H10F77/16—Material structures, e.g. crystalline structures, film structures or crystal plane orientations
    • H10F77/169—Thin semiconductor films on metallic or insulating substrates
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to a thin film-type stretchable electronic device including a stretchable substrate and a method for manufacturing the same, and more particularly, to a substrate surface-treated by surface treatment of the stretchable substrate and the bonding force between adjacent layers (Work of adhesion, Wa, mJ /m2) and surface roughness are optimized to interact with each device component layer even under a tensile strain condition to improve interlayer adhesion and realize high mechanical elasticity so that the device component layer is not damaged.
  • Thin film stretchable electronics including a stretchable substrate It relates to a device and a manufacturing method thereof.
  • stretchable electronic devices In order to be applied to the wearable device, implementation of stretchable electronic devices is required.
  • the stretchable electronic devices refer to devices that have elasticity against tensile stress and do not exhibit deterioration in electrical properties even in a tensile strain state.
  • the tensile strain limit of the silicon semiconductor thin film can be improved to about 100%, but since it is a heterojunction structure with an elastic substrate, destruction of the material may occur at larger strains, and the existing two-dimensional planar element There is no structural compatibility with
  • the main strategy for implementing the substrate stretchability requirements in stretchable solar cells is, first, a buckling strategy that forms wrinkles on the surface by contracting after attaching to a pre-stretched substrate.
  • non-patent document 1 discloses a pre-stretching or buckling method, which is compressed along the stretching direction under conditions without external strain, and when strain is applied, the compression is released. , and the device is unidirectionally elongated.
  • the above method can improve the elasticity of the device as a whole, the manufacturing process is complicated, and in particular, in the case of the pre-stretching method, there is a problem that the stretching direction is stretched only in a predetermined direction, and the buckling method has a problem in that the light receiving area As an approach from the structural aspect accompanied by this reduced structural deformation, only a certain portion is provided with elasticity, so the entire material does not reach the stretchable component.
  • an island-interconnect strategy has been developed in which the tensile properties of the device are improved only with the stretchable electrode by selectively separating the rigid region and the flexible region.
  • the stretchable concentrating solar cell disclosed in Patent Document 1 includes a substrate layer composed of a stretchable substrate and a light guide substrate; a solar battery cell installed on the light guide base unit; an insulating layer that insulates the solar cell so as to be sealed; And by including a wiring layer electrically connected to the solar cell on the insulating layer, by installing the light concentrating solar cell and the light guide material on the stretchable material, the light concentrating efficiency is increased, and design through the stretchable feature It is reported that there is an advantage that can be used in various places by improving the degree of freedom.
  • the conventional approach for providing stretchable electronic devices is an island-interconnect method in which structures are introduced by modifying existing materials or circuit connection lines are made “stretchable.” There is a problem such as a large reduction in efficiency under repeated tensile strain conditions.
  • the inventors of the present invention interact with each device component layer even under a tensile strain condition by controlling the physical properties of a substrate that mechanically supports layers on the scale of tens to hundreds of nanometers.
  • the present invention was completed by confirming high mechanical elasticity so as not to damage the device component layer by improving interlayer bonding strength.
  • An object of the present invention is to provide a thin-film stretchable electronic device including a stretchable substrate.
  • Another object of the present invention is to provide a method for manufacturing a thin-film stretchable electronic device including a stretchable substrate.
  • the present invention provides a dispersion component ( ⁇ s d ) and a polar component ( ⁇ s p ) of the substrate surface-treated by surface treatment of the stretchable substrate.
  • ⁇ s d dispersion component
  • ⁇ s p polar component
  • the surface energy of the surface-treated substrate and the surface energy of the adjacent layer calculated according to Equation 1 below, the work of adhesion (Wa) between the surface-treated substrate and the adjacent layer according to Equation 2 below is 100 to 150
  • a thin-film stretchable electronic device controlled by mJ/m 2 is provided.
  • the ⁇ is a contact angle measurement value in a DM (Diiodomethane) solution and water of the surface-treated substrate,
  • ⁇ L is the surface energy of the liquid phase
  • ⁇ L is ⁇ L d + ⁇ L p
  • ⁇ L d is the surface energy of the DM solution as a dispersive component
  • ⁇ L p is a polar component and is the literature value for the surface energy of water.
  • the ⁇ s d and ⁇ s p are the surface energies of the surface-treated substrate in the DM solution and water
  • the ⁇ SL d and ⁇ SL p are the surface energies of the adjacent layer in the DM solution and water.
  • stretchable substrate of the present invention is thermoplastic polyurethane (TPU), Thermoplastic or Thermosetting Copolymer, Polydimethylsiloxane (PDMS), Acrylic Foam Tape (AFT), Silicone Elastomer, Polyimide, Polyethylene Isopthalate, Polyethylene Naphthalate, Polyethylene Terephthalate, At least one selected from the group consisting of cellulose, shape memory polymer, and hydrogel may be used.
  • TPU thermoplastic polyurethane
  • PDMS Polydimethylsiloxane
  • AFT Acrylic Foam Tape
  • Silicone Elastomer Polyimide
  • Polyethylene Isopthalate Polyethylene Naphthalate
  • Polyethylene Terephthalate At least one selected from the group consisting of cellulose, shape memory polymer, and hydrogel may be used.
  • the stretchable substrate in a method of manufacturing a thin film stretchable electronic device including a stretchable substrate, is surface-treated, but the bonding force between the surface-treated substrate and adjacent layers calculated by Equation 1 below (work of adhesion) , Wa) is surface treated to satisfy 100 to 150 mJ/m2, and then a plurality of layers are laminated on the surface-treated substrate.
  • the surface treatment is performed so that the roughness of the substrate is 5 nm or less, and surface treatment by any one means selected from oxygen plasma treatment, ultraviolet ozone treatment, or RIE (reactive ion etching) surface treatment will be.
  • the present invention provides a wearable electronic device including a thin film stretchable electronic device including the stretchable substrate.
  • a wearable electronic device in which the thin-film stretchable electronic device is applied to any one selected from the group consisting of a sensor, an electronic skin, a flexible display, and a stretchable display.
  • the present invention includes a thin-film stretchable electronic device including a stretchable substrate, wherein the stretchable substrate is subjected to surface treatment by optimizing bonding force (Wa) and surface roughness between a stretchable substrate and an adjacent layer, thereby forming a tensile deformation state. It is possible to provide a thin-film stretchable electronic device in which high mechanical elasticity is realized so that the device component layer is not damaged by interacting with each device component layer even under conditions to improve interlayer bonding strength, and the performance of the entire device is improved.
  • Wa bonding force
  • the thin film stretchable electronic device including the stretchable substrate of the present invention is useful for application to wearable electronic devices such as a wearable computer and an electronic skin (E-skin).
  • FIG. 5 is a stress-strain curve for the film of FIG. 4;
  • Figure 6 is It shows the PCE change rate according to the strain strain (%) for the organic solar cell including the fluorine-treated substrate according to the comparative example of the present invention
  • Figure 7 is The correlation between the bonding force between the fluorine-treated substrate and the lower electrode according to the comparative example and the stretchable performance at PCE 70 is shown
  • FIG. 8 shows a correlation between bonding strength between an oxygen plasma-treated substrate and an adjacent layer and stretchable performance according to substrate roughness.
  • the present invention relates to surface control for a substrate that mechanically supports layers on the scale of tens to hundreds of nanometers among electronic devices, and by controlling the surface energy through surface treatment of the stretchable substrate, bonding strength between adjacent layer interfaces is improved. It is possible to improve the stretchability of a thin film stretchable electronic device including a stretchable substrate.
  • a device including a stretchable substrate must have high mechanical elasticity and robustness so that the component layers of the device are not damaged even when stretched, and at the same time, the component layers of the device must be well bonded.
  • the present invention is a thin film stretchable electronic device including a stretchable substrate, the dispersion component ( ⁇ s d ) and polar component ( ⁇ s ) of the substrate surface-treated by surface treatment of the stretchable substrate
  • the surface energy between p ) is calculated according to Equation 1 below,
  • the surface energy of the surface-treated substrate and the surface energy of the adjacent layer calculated according to Equation 1 below, the work of adhesion (Wa) between the surface-treated substrate and the adjacent layer according to Equation 2 below is 100 to 150
  • a thin-film stretchable electronic device controlled by mJ/m 2 is provided.
  • the ⁇ is a contact angle measurement value in a DM (Diiodomethane) solution and water of the surface-treated substrate,
  • ⁇ L is the surface energy of the liquid phase
  • ⁇ L is ⁇ L d + ⁇ L p
  • ⁇ L d is the surface energy of the DM solution as a dispersive component
  • ⁇ L p is a polar component and is the literature value for the surface energy of water.
  • the ⁇ s d and ⁇ s p are the surface energies of the surface-treated substrate in the DM solution and water
  • the ⁇ SL d and ⁇ SL p are the surface energies of the adjacent layer in the DM solution and water.
  • the bonding force (Wa) of the present invention is a value calculated from the surface energy and contact angle between the surface-treated substrate and the adjacent layer, and the surface energy is the surface energy ( ⁇ d ) and polarity generated by the instantaneous bias of electric charges between molecules. It is obtained as the sum of surface energies ( ⁇ p ) generated by the bias of electric charges generated between molecules.
  • the bonding force (Wa) between the surface-treated substrate and the adjacent layer is improved by 30 to 45% compared to the untreated substrate, so it can be confirmed that the bonding force between the layers is improved.
  • the surface treatment can be performed by any means capable of controlling the surface energy and contact angle of the substrate, and is preferably performed by any one method selected from oxygen plasma treatment, ultraviolet ozone treatment, or RIE (reactive ion etching) surface treatment. And, more preferably, in the embodiment, it is described as controlling surface properties by oxygen plasma treatment, but it will not be limited thereto.
  • the surface treatment When surface treatment is performed with the oxygen plasma, it is preferable to perform the surface treatment at a plasma intensity of 40 to 90 W, more preferably at 65 to 90 W, and the irradiation time is within 5 to 10 minutes, more preferably within 5 minutes. However, it can be changed according to the equipment used or conditions.
  • the surface roughness (RMS) of the surface-treated substrate is 5 nm or less.
  • the surface roughness (RMS) of the surface-treated substrate exceeds 5 nm, the surface is rough and non-uniform, and a large force is applied to the bonding surface. The efficiency of the device is drastically reduced.
  • the intensity or time conditions of the oxygen plasma may be selected within a range in which the surface roughness of the surface-treated substrate is 5 nm or less.
  • the bonding force or surface roughness of the surface-treated substrate is satisfied, it can be selected from the elastomer material group.
  • thermoplastic polyurethane TPU
  • Thermoplastic or Thermosetting Copolymer Polydimethylsiloxane (PDMS), Acrylic Foam Tape (AFT), Silicone Elastomer
  • PDMS Polydimethylsiloxane
  • AFT Acrylic Foam Tape
  • Silicone Elastomer Polyimide
  • Polyethylene Isopthalate Polyethylene Naphthalate
  • Polyethylene Terephthalate It includes a single form selected from the group consisting of cellulose, a shape memory polymer, and a hydrogel, or a mixture thereof.
  • thermoplastic copolymer is a styrene-butadiene copolymer (SB), a styrene-butadiene-styrene copolymer (SBS), a styrene-isoprene-styrene copolymer (styrene-isoprene- At least one selected from the group consisting of styrene copolymer (SIS), styrene-ethylene-butylene-styrene copolymer (SEBS) and styrene-butadiene rubber (SBR) can include
  • thermoplastic polyurethane TPU
  • PDMS polydimethylsiloxane
  • examples of thin-film stretchable electronic devices include organic/inorganic solar cells, thin-film transistors, optoelectronic devices, and the like.
  • the present invention will be described centering on an organic solar cell including a charge transport layer, an organic photoactive layer made of a conjugated polymer, and an electrode layer made of a stretchable conductor on a stretchable substrate, but it will not be limited thereto.
  • the organic solar cell implemented in the embodiment of the present invention is a conventional organic solar cell structure in which multiple layers are formed around a photoactive layer formed on a surface-treated stretchable substrate, and polymer-based or low-molecular-weight holes constituting the charge transport layer
  • the location of the transport layer or the polymer-based or low-molecular-weight electron transport layer may be reversed up and down, and since the first electrode layer and the second electrode layer constituting the electrode layer may also be mutually inverted as a lower electrode and an upper electrode, a normal structure or an inverted (inverted) structure.
  • the structure in which the first electrode layer, the hole transport layer, the photoactive layer, the electron transport layer, and the second electrode layer are sequentially formed on the surface-treated stretchable substrate has been described, but the structure in which the first electrode layer and the second electrode layer are bonded is described above. It will also be possible to provide an organic solar cell having a structure in which the positions of the hole transport layer and the electron transport layer are mutually inverted.
  • the charge transport layer includes an organic transport layer, an inorganic transport layer, and a transport layer made of a combination of the organic and inorganic transport layers, and more preferably, a polymer-based hole transport layer, a low-molecular-weight hole transport layer, a polymer-based electron transport layer, and a low-molecular electron transport layer. It may include a transport layer made of an organic system consisting of a single or mixed form selected from the transport layer.
  • PCE performance can be improved when a polymer-based hole transport layer (HTL) and a polymer-based electron transport layer (ETL) are simultaneously included.
  • HTL polymer-based hole transport layer
  • ETL polymer-based electron transport layer
  • the polymer-based hole transport layer is PEDOT: PSS (poly (3,4-ethylenedioxythiophene): poly (styrene sulfonate)), polyacetylene, polypyrrole, polyparaphenylene, polyaniline, polythiophene group, poly It includes one or two or more selected from the group consisting of a triarylamine group, a conjugated polyelectrolyte-based polymer, a tetraphenyldiamine group crosslinkable polymer, and a bis(trimethylsilyl)amine-based polymer.
  • PSS poly (3,4-ethylenedioxythiophene): poly (styrene sulfonate)
  • polyacetylene polypyrrole
  • polyparaphenylene polyaniline
  • polythiophene group poly It includes one or two or more selected from the group consisting of a triarylamine group, a conjugated polyelectrolyte-based polymer, a t
  • the polytriarylamine group includes poly(triaryl amine) (PTAA) or Poly(9,9-dioctylfluorene-alt-N-(4-sec-butylphenyl)-diphenylamine) (TFB), and conjugated polyelectrolyte ) series of polymers, CPE-K can be used.
  • PTAA poly(triaryl amine)
  • TFB Poly(9,9-dioctylfluorene-alt-N-(4-sec-butylphenyl)-diphenylamine)
  • CPE-K conjugated polyelectrolyte
  • the polymer-based electron transport layer (ETL) forming solution is PNDIT-F3N-Br (Poly[[2,7-bis(2-ethylhexyl)-1,2,3,6,7,8-hexahydro-1, 3,6,8-tetraoxobenzo[lmn][3,8]phenanthroline-4,9-diyl]-2,5-thiophenediyl[9,9-bis[3'((N,N-dimethyl)-N-ethylammonium )]propyl]-9H-fluorene-2,7-diyl]-2,5-thiophenediyl]), PFN (Poly [(9,9-bis(3'-(N,N-dimethylamino)propyl)-2, 7-fluorene)-alt-2,7-(9,9-dioctylfluorene)]).
  • the photoactive layer is an organic photoactive layer, which is selected from the group consisting of a polymer conjugated donor, a low molecular weight conjugated donor, a polymer conjugated acceptor, and a low molecular weight conjugated acceptor, or a combination of two or more thereof.
  • a polymer conjugated donor a low molecular weight conjugated donor
  • a polymer conjugated acceptor a polymer conjugated acceptor
  • a low molecular weight conjugated acceptor or a combination of two or more thereof.
  • An example of a case in which two or more species are combined is a polymeric conjugated donor and a polymeric conjugated acceptor, a conjugated low molecular weight acceptor, or a conjugated acceptor of a mixture including the two.
  • Various combinations are possible. However, in the case of the above alone, it is made of a polymer conjugated compound.
  • the conjugated acceptor includes poly(para-phenylene), polyacetylene, polypyrrole, polyvinylcarbazole, polyaniline and polyphenylenevinylene, fullerene and non-fullerene acceptors. A single form or a mixture of two or more selected from the group consisting of is used.
  • the weight ratio of the polymeric conjugated donor and the conjugated acceptor forming the photoactive layer is 1:10 to 10:1, preferably, the weight ratio of the polymeric conjugated donor and the conjugated acceptor is 1:5 to 5:1, and more preferably, the weight ratio of the polymer conjugated donor and the conjugated acceptor is 1:3 to 3:1.
  • the weight ratio of the polymer conjugated donor and the conjugated acceptor is an important factor in optimizing mechanical robustness and elasticity, and if the weight ratio is exceeded, brittleness may increase.
  • the electrode layer includes a first electrode layer and a second electrode layer, and if one electrode layer selected from the first electrode layer or the second electrode layer constituting the electrode layer is a lower electrode formed adjacent to the substrate, , another electrode layer is formed as an upper electrode, and its position can be mutually reversed.
  • the first electrode layer or the second electrode layer is made of a stretchable conductor selected from polymers or stretchable metals, excellent stretchability is realized.
  • the first electrode layer or the second electrode layer is made of a polymer of PEDOT:PSS (poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate))
  • the first electrode layer or the second electrode layer is preferably acid treated, More preferably, one or more additives selected from the group consisting of dimethyl sulfoxide (DMSO), polyethylene glycol (PEG), and fluorine-based surfactants may be further included.
  • DMSO dimethyl sulfoxide
  • PEG polyethylene glycol
  • fluorine-based surfactants may be further included.
  • the first electrode layer or the second electrode layer is made of a stretchable conductor containing a stretchable metal.
  • the EGaIn liquid metal is micronized to
  • the first electrode layer or the second electrode layer can be formed in a fine pattern ( ⁇ 200 ⁇ m) shape without any damage to the entire surface of the lower layer by spray printing in a liquid phase.
  • first electrode layer or the second electrode layer of the present invention may be mixed with known flexible/stretchable electrode materials such as silver nanowires (AgNW) and carbon nanotubes (CNT), as well as liquid metal.
  • known flexible/stretchable electrode materials such as silver nanowires (AgNW) and carbon nanotubes (CNT), as well as liquid metal.
  • stretchable substrate (TPU) / first electrode layer (PEDOT: PSS, PH1000) / hole transport layer (PEDOT: PSS, AI4083) / organic photoactive layer (PM6: Y7)/electron transport layer (PNDIT-F3N-Br)/second electrode layer (EGaIn) are bonded to each other to form a normal organic solar cell.
  • Figure 2 is For an organic solar cell including a plasma-treated substrate according to an embodiment of the present invention, the PCE change rate according to the strain strain is shown, based on the PCE 70 point at which the efficiency reaches 70% compared to the initial efficiency, the plasma treatment If not, while enduring 30% strain until reaching the PCE 70 point, organic solar cells including substrates surface-treated by oxygen plasma treatment under different conditions show improved device elasticity. Most preferably, the organic solar cell including the substrate treated with oxygen plasma at 90 W for 5 minutes endures 90% strain until reaching the PCE 70 point and achieves PCE 54.3% efficiency when strain is applied up to 120%.
  • device elasticity increases under the condition that the bonding force (Wa) increases and the surface roughness (RMS) of the surface-treated substrate satisfies 5 nm or less. trend can be identified.
  • FIG. 3 shows the correlation between the bonding force between the plasma-treated substrate and the lower electrode and the stretchable performance at PCE 70 .
  • the bonding force is affected by the surface functional group and the surface roughness.
  • the etching phenomenon tends to increase due to the collision between the radical and the substrate.
  • the bonding force with the lower electrode (PH1000), one of the polar element component layers during oxygen plasma treatment is not proportional to the oxygen plasma strength under the roughness condition of 5 nm or less. It shows the smallest value at 65W for 5 minutes, the next largest value at 40W for 5 minutes, and the largest value at 90W for 5 minutes.
  • PM6 This is the result of finite element analysis of the 3D model visualizing the tensile stress distribution according to stretching for the single film made of Y7).
  • FIG. 5 is A stress-strain curve for the film of FIG. 4 is shown.
  • the single film composed of the photoactive layer (PM6:Y7) showed a strain at break of 2.76%
  • the film with the photoactive layer (PM6:Y7) attached on the PEDOT:PSS surface showed a strain at break of 9.64%. .
  • the photoactive layer with strong interfacial adhesion can be easily bonded to the adhering layer.
  • the strain tends to be evenly distributed in the photoactive layer when deformation occurs, and thus the photoactive layer can withstand much greater deformation than when it exists as an independent film.
  • the organic solar cell prepared in the embodiment of the present invention can achieve durability that maintains more than 70% of the initial PCE even after repeated tensile deformation while satisfying excellent PCE performance through smooth interfacial bonding between stretchable components of each layer. there is. More specifically, the organic solar cell prepared in Example 1 implements an excellent PCE of 11% or more, and maintains 80% or more of the initial PCE in 100 to 10,000 tensile repetition tests under a 10% tensile external force condition. see.
  • the organic solar cell of the present invention induces excellent interfacial bonding between the components of each layer as each layer is made of a stretchable material and seamlessly integrates them into a single system, so that it It is not limited to, and implements stretchable characteristics having elasticity and restoring force at a level that can be freely deformed regardless of the direction or more than the biaxial direction.
  • the surface roughness (RMS) of the contact heap and the surface-treated substrate is 5
  • the organic solar cell manufactured under the control of nm or less can be applied to all maintenance solar cells having a predetermined PCE performance by realizing a result in which 70% or more of the initial PCE was maintained in 100 to 10,000 repeated tensile tests.
  • an organic solar cell having a PCE performance of 5% or more, preferably 10% or more may be included.
  • FIG. 6 For an organic solar cell including a substrate treated with fluorine according to a comparative example of the present invention, PCE change rate according to strain strain is shown, and FIG. 7 is The correlation between the bonding force between the fluorine-treated substrate and the lower electrode according to the comparative example and the stretchable performance at PCE 70 is shown.
  • fluorine treatment is not preferable as a surface treatment method, and when the substrate roughness is equally controlled, the lower the bonding force, the more the strain strain (%) that can be endured until reaching the PCE 70 point during stretching means lower
  • the present invention is a method for manufacturing a thin film stretchable electronic device including a stretchable substrate, wherein the stretchable substrate is surface-treated, and the junction calculated by Equation 1 from the contact angle or surface energy between the surface-treated substrate and adjacent layers Work of adhesion (Wa) is 100 to 150 After surface treatment to satisfy mJ/m 2 , a method of manufacturing a thin-film stretchable electronic device is provided by laminating a plurality of layers on the surface-treated substrate.
  • the surface treatment is performed so that the roughness of the substrate is 5 nm or less.
  • a preferable surface treatment method may be performed by any one means selected from oxygen plasma treatment, ultraviolet ozone treatment, or RIE (reactive ion etching) surface treatment, and surface treatment methods that lower surface energy, such as fluorine treatment, are excluded. .
  • the present invention provides a wearable electronic device including a thin film stretchable electronic device including the stretchable substrate.
  • the thin-film stretchable electronic device can be applied to various electronic devices such as various sensors including strain sensors, temperature sensors, pressure sensors, optical sensors, vibration sensors, and biosensors, electronic skins, flexible displays, and stretchable displays.
  • various sensors including strain sensors, temperature sensors, pressure sensors, optical sensors, vibration sensors, and biosensors, electronic skins, flexible displays, and stretchable displays.
  • it can be applied to clothing-type, accessory-type, or body-attached wearable electronic devices targeting skin, textiles, or curved surfaces.
  • thermoplastic polyurethane (TPU) substrate (Afel Company) was prepared and subjected to surface treatment at an oxygen plasma intensity of 65 W for 5 minutes.
  • a solution containing PEDOT:PSS (Heraeus CleviosTM PH1000) was filtered through a 0.45 ⁇ m filter on the surface-treated substrate, and then spin-coated in air (2000 rpm) to form a first electrode layer.
  • the PEDOT:PSS (Heraeus CleviosTM PH1000) containing solution contains 5% by volume of DMSO, 2% by volume of polyethylene glycol (PEG) and 0.5% by volume of Zonyl Fluorine surfactant (Zonyl FS-30) as additives, and prior to application Stir overnight.
  • the DMSO improves the electrical conductivity of PH1000 PEDOT:PSS, PEG improves the mechanical elasticity, and FS-30 increases the surface wettability.
  • the PH1000 film was treated with citric acid, a weak acid, to improve conductivity by increasing the crystallinity of the PEDOT domain.
  • the stretchable substrate was plasma-treated before spin coating to improve wettability with the PH1000 film.
  • the TPU substrate coated with PEDOT:PSS (PH1000) was heated in air at 100°C for 20 minutes to dry the residue, then cooled, treated with citric acid for PH1000 at 100°C for 20 minutes, spin-coated again, and dried. did
  • TPU/PEDOT:PSS PH1000
  • PEDOT:PSS Heraeus CleviosTM AI4083
  • PM6, 1-Materials represented by the following formula (1)
  • Y7, Derthon non-fullerene acceptor
  • a blend of PM6:Y7 (1:1, w/w) and CB (containing 0.5% by volume of CN) and a total concentration of 20 mg/ml were spin-coated at 2000 rpm for 40 seconds, followed by PNDIT-F3N with a total concentration of 1 mg/ml.
  • a -Br solution was prepared in methanol, stirred for 6 hours and then spin-coated onto the photoactive layer at 2000 rpm for 40 seconds. At this time, a small piece of PDMS film was used to pattern the photoactive layer and electron transport layer (ETL) on the TPU film.
  • ETL electron transport layer
  • Oxygen plasma treatment of the thermoplastic polyurethane (TPU) substrate was performed in the same manner as in Example 1, except that surface treatment was performed at a plasma intensity of 45 W for 5 minutes.
  • Oxygen plasma treatment of the thermoplastic polyurethane (TPU) substrate was performed in the same manner as in Example 1, except that surface treatment was performed at a plasma intensity of 90 W for 5 minutes.
  • Example 2 It was carried out in the same manner as in Example 1, except that a synthetic polydimethylsiloxane (PDMS) substrate (surface roughness of 3 nm) was used instead of the thermoplastic polyurethane (TPU) substrate.
  • PDMS polydimethylsiloxane
  • TPU thermoplastic polyurethane
  • thermoplastic polyurethane (TPU) substrate It was carried out in the same manner as in Example 1 without oxygen plasma treatment of the thermoplastic polyurethane (TPU) substrate.
  • Oxygen plasma treatment of the thermoplastic polyurethane (TPU) substrate was performed in the same manner as in Example 1, except that surface treatment was performed at a plasma intensity of 90 W and for 15 minutes.
  • Oxygen plasma treatment of the thermoplastic polyurethane (TPU) substrate was performed in the same manner as in Example 1, except that surface treatment was performed at a plasma intensity of 65 W and for 15 minutes.
  • thermoplastic polyurethane (TPU) substrate was treated with fluorine (F 2 :N 2 ratio).
  • the surface energy of the substrate is shown in Table 1 by calculating the bonding force between the surface-treated substrate and the lower electrode PH1000 performed in the above example by Equations 1 and 2 below. Specifically, from the surface energy of the surface-treated substrate and the surface energy of the adjacent layer calculated according to Equation 1 below, the work of adhesion (Wa) between the surface-treated substrate and the adjacent layer is calculated according to Equation 2 below. .
  • Equation 1 ⁇ is the contact angle measurement value of the DM solution and water of the surface-treated substrate, ⁇ L is the surface energy of the liquid phase, ⁇ L is the calculated value of ⁇ L d + ⁇ L p , and ⁇ s is the substrate As the surface energy of , ⁇ s is the calculated value of ⁇ s d + ⁇ s p .
  • ⁇ L d is the surface energy of the DM solution as a dispersion component (dispersion, d)
  • ⁇ L p is a literature value for the surface energy of water as a polar component (polar, p).
  • ⁇ L p is 2.3 mJ/m 2 and ⁇ L d is 48.5 mJ/m 2
  • ⁇ L p is 50.3 mJ/m 2
  • ⁇ L d is 22.85 mJ/m 2
  • ⁇ s d and ⁇ s p are surface energies in DM solution and water of the surface-treated substrate
  • ⁇ SL d and ⁇ SL p are surface energies in DM solution and water of adjacent layers.
  • the bonding force was calculated based on the surface energy of the substrate, and the surface roughness was shown in Table 2 through a surface roughness measuring instrument.
  • FIG. 2 shows the PCE change rate according to the strain strain (%) for an organic solar cell including a substrate plasma-treated under the above conditions
  • FIG. 3 shows the bonding force between the plasma-treated substrate and the lower electrode and the PCE 70 The correlation between the stretchable performance in is shown.
  • the surface energy of the lower electrode is ⁇ s p of 30.8, ⁇ s d is 32.8, ⁇ s was 63.1.
  • FIG. 6 shows the PCE change rate according to the strain strain (%) for the organic solar cell including the fluorine-treated substrate according to the comparative example
  • FIG. 7 shows the bonding force between the fluorine-treated substrate and the lower electrode. and the correlation between stretchable performance at PCE 70 is shown. 6 and 7, it was shown that the bonding strength between the fluorine-treated substrate and the lower electrode decreased as the ratio of fluorine increased. In particular, when treated with fluorine, it shows a lower strain strain (%) until reaching the PCE 70 point when treated with fluorine than untreated thermoplastic polyurethane (TPU), so fluorine treatment is not preferred as a surface treatment method. confirmed.
  • TPU thermoplastic polyurethane

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Abstract

La présente invention concerne une électronique extensible de type à couche mince comprenant un substrat extensible et son procédé de fabrication. La présente invention concerne une électronique extensible de type à couche mince dans laquelle, par le traitement de surface d'un substrat extensible, une rugosité de surface et le travail d'adhérence (Wa, mJ/㎡) entre le substrat traité en surface et une couche adjacente sont optimisés de telle sorte que, par une interaction entre des couches constitutives de dispositif, même dans des conditions d'allongement en traction, le travail d'adhérence entre les couches est amélioré, ce qui permet d'assurer une extensibilité mécanique élevée pour éviter des dommages aux couches constitutives de dispositif. L'électronique extensible de type à couche mince est utile pour une application à des dispositifs électroniques à porter sur soi.
PCT/KR2022/015255 2021-11-01 2022-10-11 Électronique extensible de type à couche mince comprenant un substrat extensible et son procédé de fabrication Ceased WO2023075201A1 (fr)

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KR102379648B1 (ko) * 2021-11-01 2022-03-29 한국과학기술원 신축성 기판을 포함하는 박막형 신축성 전자소자 및 그의 제조방법
CN115742513B (zh) * 2022-11-14 2025-04-22 哈尔滨工业大学 一种形状记忆柔性传感器、制备方法及应用

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EP3200195A1 (fr) * 2014-09-23 2017-08-02 Corning Precision Materials Co., Ltd. Substrat flexible et son procédé de fabrication
WO2018081705A1 (fr) * 2016-10-31 2018-05-03 The Regents Of The University Of California Procédé et structure de niveau de distribution en éventail de tranches flexible
KR101899253B1 (ko) * 2017-07-07 2018-10-31 한국광기술원 스트레처블 집광형 태양전지 및 이의 제조방법
KR102293405B1 (ko) * 2020-02-24 2021-08-26 연세대학교 산학협력단 스트레처블 발광소재를 이용한 유기전계 발광소자 및 그 제조방법
KR20210128905A (ko) * 2020-04-17 2021-10-27 한국과학기술원 소재고유형 스트레쳐블 유기태양전지, 그의 제조방법 및 그를 포함한 전자장치
KR102379648B1 (ko) * 2021-11-01 2022-03-29 한국과학기술원 신축성 기판을 포함하는 박막형 신축성 전자소자 및 그의 제조방법

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3200195A1 (fr) * 2014-09-23 2017-08-02 Corning Precision Materials Co., Ltd. Substrat flexible et son procédé de fabrication
WO2018081705A1 (fr) * 2016-10-31 2018-05-03 The Regents Of The University Of California Procédé et structure de niveau de distribution en éventail de tranches flexible
KR101899253B1 (ko) * 2017-07-07 2018-10-31 한국광기술원 스트레처블 집광형 태양전지 및 이의 제조방법
KR102293405B1 (ko) * 2020-02-24 2021-08-26 연세대학교 산학협력단 스트레처블 발광소재를 이용한 유기전계 발광소자 및 그 제조방법
KR20210128905A (ko) * 2020-04-17 2021-10-27 한국과학기술원 소재고유형 스트레쳐블 유기태양전지, 그의 제조방법 및 그를 포함한 전자장치
KR102379648B1 (ko) * 2021-11-01 2022-03-29 한국과학기술원 신축성 기판을 포함하는 박막형 신축성 전자소자 및 그의 제조방법

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