WO2023202390A1 - Photoresist composition and method for patterning device - Google Patents

Photoresist composition and method for patterning device Download PDF

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Publication number
WO2023202390A1
WO2023202390A1 PCT/CN2023/086787 CN2023086787W WO2023202390A1 WO 2023202390 A1 WO2023202390 A1 WO 2023202390A1 CN 2023086787 W CN2023086787 W CN 2023086787W WO 2023202390 A1 WO2023202390 A1 WO 2023202390A1
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Prior art keywords
monomer
photoresist composition
formula
group
layer
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PCT/CN2023/086787
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French (fr)
Chinese (zh)
Inventor
蔡承恩
陈旻贤
刘玲均
林文福
朱克泰
陈慧修
Original Assignee
台州观宇科技有限公司
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Priority claimed from CN202210975763.2A external-priority patent/CN116954021A/en
Application filed by 台州观宇科技有限公司 filed Critical 台州观宇科技有限公司
Publication of WO2023202390A1 publication Critical patent/WO2023202390A1/en

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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials

Definitions

  • the present disclosure relates to a photoresist composition and a method of patterning a device using the photoresist composition.
  • OLED organic light-emitting diode
  • LCD organic light-emitting diode
  • OLED light-emitting diode
  • OLED can be used in display devices, such as TV screens, computer screens, mobile phones, tablets, smart watches and smart glasses.
  • OLED devices are self-illuminating devices and have been widely discussed due to their brightness, better visibility, and ability to display clearer images than LCD devices.
  • a photoresist composition includes: a polymer composed of a first monomer and a first Polymerized from two monomers, the first monomer is an acrylic monomer containing a polymerizable group and a fluorine-containing group, and the second monomer is an acrylic monomer containing a polymerizable group and a reactive group that can change the solubility.
  • a group of monomers a photobase generator; a thermal acid generator; and a fluorinated solvent.
  • a method of patterning a device includes forming a photoresist composition layer on a substrate of a device, the photoresist composition layer including a photoresist composition, the The photoresist composition includes a polymer polymerized from a first monomer and a second monomer, wherein the first monomer is an acrylic monomer containing a polymerizable group and a fluorine-containing group.
  • the second monomer is a monomer containing a polymerizable group and a solubility-changing reactive group, a photobase generator, a thermal acid generator, and a first fluorinated solvent; exposing the photoresist composition subjecting the photoresist composition layer to patterned radiation to form an exposed area and an unexposed area; baking the exposed area and the unexposed area; and removing the photoresist composition layer
  • the exposure area forms a development structure.
  • Figure 1 is a flowchart of a method of patterning a device in accordance with certain embodiments of the present disclosure.
  • Figure 2 is a top view of a device according to a method of patterning a device in accordance with certain embodiments of the present disclosure.
  • 3-10 are cross-sectional views of a device structure during various stages according to certain embodiments of the present disclosure.
  • a key challenge in OLED devices is to pattern arrays of red, green, and blue pixels, and each pixel contains easily damaged and sensitive organic compound materials. Therefore, the art needs to come up with an effective and non-damaging OLED A method of patterning a device.
  • the present disclosure provides a photoresist composition, including: a polymer polymerized from a first monomer and a second monomer, wherein the first monomer contains a polymerizable group An acrylic monomer with a group and a fluorine-containing group, the second monomer is a monomer containing a polymerizable group and a reactive group that can change the solubility; Photo base generator (PBG); A thermal acid generator (TAG); and a fluorinated solvent.
  • the photoresist composition is a positive photoresist.
  • the polymer is formed by free radical polymerization of a first monomer and a second monomer, and the first monomer is a monomer represented by formula (I):
  • R 1 represents a hydrogen atom, a cyano group, a methyl group or an ethyl group
  • R 2 represents a substituted or unsubstituted alkyl group having at least 5 fluorine atoms.
  • R is a substituted or unsubstituted alkyl group of at least 10 fluorine atoms.
  • the alkyl group of R2 is a cyclic or acyclic hydrofluorocarbon or hydrofluoroether having at least as many fluorine atoms as carbon atoms.
  • R represents a perfluoroalkyl group having at least 4 carbon atoms or a 1H, 1H, 2H, 2H-perfluoroalkyl group.
  • the 1H, 1H, 2H, 2H-perfluoroalkyl group may be, for example, but not limited to, 1H, 1H, 2H, 2H-perfluorooctyl methacrylate (FOMA for short).
  • the first monomer is a monomer represented by formula (I-1):
  • the second monomer is a monomer represented by formula (II):
  • R 3 represents a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms. In certain embodiments, R3 is tertiary alkyl. In certain embodiments, the monomer represented by formula (II) is selected from the group consisting of: formula (II-1), formula (II-2), formula (II-3), formula (II-4) ), or formula (II-5)
  • the second monomer is a monomer represented by formula (II-2).
  • the polymer is formed through free radical polymerization.
  • a thermal initiator that can undergo pyrolysis to generate free radicals, and performing free radical polymerization under certain polymerization conditions.
  • the thermal initiator may be, for example, but not limited to, 2,2'-Azobis (isobutyronitrile), AIBN for short.
  • the polymer is formed by reacting the monomer represented by formula (I-1) and the monomer represented by formula (II-2) as follows, so that the polymer contains the structure shown below:
  • the thermal acid generator is selected from the group consisting of: Para-Toluene-Sulfonic Acid (pTSA for short), Dodecyl Benzene Sulfonic Acid (Dodecyl Benzene Sulfonic Acid for short) DDBSA), Fluoroantimonic acid (SbF 6 ), Triflate group (-OTf), and Tris(pentafluorophenyl)borane (TPFB) ).
  • pTSA Para-Toluene-Sulfonic Acid
  • Dodecyl Benzene Sulfonic Acid Dodecyl Benzene Sulfonic Acid for short
  • DDBSA Dodecyl Benzene Sulfonic Acid
  • SbF 6 Fluoroantimonic acid
  • -OTf Triflate group
  • TPFB Tris(pentafluorophenyl)borane
  • the photobase generator is selected from the group consisting of: formula (III-1), formula (III-2), formula (III-3), formula (III-4), or Formula (III-5)
  • the photoresist composition does not include a photoacid generator.
  • fluorinated solvents include room temperature perfluorinated or highly fluorinated solvents that are immiscible with water and most organic solvents.
  • the fluorinated solvent may be, for example, but not limited to, hydrofluoroether (HFE), which is highly environmentally friendly and has the title of "green” solvent.
  • HFE hydrofluoroether
  • HFE including isolated HFE is non-flammable, has zero ozone depletion potential, and has been shown to have very low toxicity to humans.
  • HFE and isomeric mixtures of HFE may be, for example, but not limited to, methyl nonafluorobutyl ether and methyl nonafluoroisobutyl ether (HFE-7100), ethanol.
  • Isomeric mixture of nonafluorobutyl ether and ethyl nonafluoroisobutyl ether HFE-7200aka Novec TM 7200
  • 3-ethoxy-1,1,1,2,3,4,4, 5,5,6,6,6-dodecafluoro-2-trifluoromethyl-hexane HFE-7500aka Novec TM 7500
  • 1,1,1,2,3,3-hexafluoro-4-( 1,1,2,3,3,3-Hexafluoropropoxy)-pentane HFE-7600aka Novec TM 7600
  • 1-methoxyheptafluoropropane HFE-7000
  • the content of the polymer ranges from The content of the photobase generator ranges from 1 to 50wt%, the content of the photobase generator ranges from 0.1 to 20wt%, the content of the thermal acid generator ranges from 0.1 to 20wt%, and the content of the fluorinated solvent ranges from 1 to 99wt%.
  • Figure 1 is a flowchart of a method of patterning a device in accordance with certain embodiments of the present disclosure.
  • the method 100 includes several operations: (101) Forming a photoresist composition layer on a substrate of a device, the photoresist composition layer includes a photoresist composition, a photoresist
  • the composition includes a polymer polymerized from a first monomer and a second monomer, wherein the first monomer is an acrylic monomer containing a polymerizable group and a fluorine-containing group, and the second monomer
  • the body is a monomer containing a polymerizable group and a solubility-changing reactive group, a photobase generator, a thermal acid generator, and a first fluorinated solvent; (102) Exposing the photoresist composition layer to Patterned radiation to form an exposed area and an unexposed area in the photoresist composition layer; (103) baking the exposed area and the unexposed area; and (104) removing the exposure of the photore
  • Figure 2 is a top view of a device processed by a method of patterning a device in accordance with certain embodiments of the present disclosure. As shown in Figure 2, a substrate 10 is provided.
  • the device processed by method 100 is an electroluminescent device. In some embodiments, the device processed by method 100 is an OLED device.
  • device substrate 10 includes display area 10D and peripheral area 10P.
  • the substrate 10 also includes a plurality of pixels 12 located in the display area 10D. Pixels 12 may be arranged in an array. Each individual pixel 12 is separated from other adjacent pixels 12 .
  • each pixel 12 includes a first sub-pixel 12A and a second sub-pixel 12B.
  • each pixel 12 includes a first sub-pixel 12A, a second sub-pixel 12B, and a third sub-pixel 12C.
  • a sub-pixel may also be referred to as a sub-pixel region or pixel.
  • the first sub-pixel 12A, the second sub-pixel 12B and the third sub-pixel 12B can be used to display different colors.
  • the first sub-pixel 12A, the second sub-pixel 12B and the third sub-pixel 12C can respectively emit a first color image, a second color image and a third color image.
  • the first sub-pixel 12A can be used to display green
  • the second sub-pixel 12B can be used to display red
  • the third sub-pixel 12C can be used to display red. Shows blue.
  • the arrangement of the sub-pixels includes, from left to right, the first sub-pixel 12A, the second sub-pixel 12B and then the third sub-pixel 12C, but is not limited thereto.
  • the arrangement of sub-pixels can also be changed based on design or other considerations.
  • the sub-pixel shape shown in FIG. 2 is square, the sub-pixels can also adopt other shapes.
  • the number of sub-pixels in the pixel 12 may be, but is not limited to, three sub-pixels; the number of sub-pixels may be changed, and other appropriate sub-pixels may be used to display different colors, such as yellow, white or other colors.
  • substrate 10 may be a rigid or flexible substrate. Furthermore, substrate 10 may be an opaque or transparent substrate. Substrate 10 may include glass, quartz, semiconductor materials (such as silicon, III-V elements), or other suitable materials. In certain embodiments, substrate 10 includes graphene. In certain embodiments, substrate 10 may be formed utilizing a polymeric matrix material. A dielectric layer (not shown in the figure) may optionally be provided on the substrate 10 . In certain embodiments, the dielectric layer may be made of silicon oxide, silicon nitride, silicon oxynitride, or other suitable materials.
  • FIG. 3-10 are cross-sectional views of a device structure during various stages according to certain embodiments of the present disclosure.
  • FIG. 3 is a schematic cross-sectional view of a pixel along line segment A-A in FIG. 2 .
  • method 100 uses the photoresist composition of the present disclosure.
  • electrode 14 is formed on substrate 10 .
  • a plurality of sub-pixels share an electrode 14 .
  • Electrode 14 may include opaque conductive material or transparent conductive material. Examples of opaque conductive materials may include a metal such as aluminum (Al), copper (Cu), silver (Ag), gold (Au), tungsten (W), another metal, or a metal alloy. Examples of transparent conductive materials may include indium tin oxide (ITO), indium zinc oxide (IZO), aluminum-doped zinc oxide (AZO) and indium-doped cadmium oxide, or other similar materials.
  • electrode 14 is the anode of the device. In some embodiments, a plurality of electrodes 14 are formed separately on the substrate 10 , and the first sub-pixel 12A and the second sub-pixel 12B respectively have different electrodes 14 . In some embodiments, each sub-image The element includes an electrode 14.
  • the substrate 10 includes a driving circuit, such as a thin film transistor (TFT) array.
  • the pattern of the electrode 14 can be designed according to the desired pixel arrangement.
  • the electrode 14 can be electrically connected to a driving circuit in the substrate 10 to receive a driving signal for driving the electroluminescent device.
  • the disclosed method of patterning a device can process multiple pixels 12 .
  • a pixel defining layer (also referred to as PDL) 16 is formed on the substrate 10 to separate the first sub-pixel 12A and the second sub-pixel 12B.
  • pixel defining layer 16 partially covers electrode 14 and leaves a portion of electrode 14 open to receive the light emitting layer.
  • the pixel defining layer 16 separates the plurality of electrodes 14 from each other when viewed through the thickness of the device.
  • Pixel defining layers 16 may have the same or different shapes. As shown in FIG. 3 , the cross-section of the pixel defining layer 16 may have a curved surface. In some embodiments, the shape of the pixel defining layer 16 may be a trapezoid, an inverted ladder, or a square. Viewed through the thickness of the device, the pixel defining layers 16 may be arranged in a grid. The pattern of the pixel defining layer 16 can be designed according to the desired pixel arrangement.
  • the pixel defining layer 16 includes a polymer material, a photosensitive material or a light-absorbing material, and its color is not particularly limited. In some embodiments, the pixel defining layer 16 is formed through a photolithography process.
  • an organic material layer 18 is formed over the pixel defining layer 16 and the electrode 14 exposed through the pixel defining layer 16 .
  • the organic material layer 18 is a first carrier injection layer, a first carrier transport layer, or a combination of the above.
  • the first carrier injection layer can be used for hole injection or electron injection.
  • the first carrier transport layer can be used for hole transport or electron transport.
  • the first carriers are holes, and the organic material layer 18 includes a hole injection layer (HIL) formed on the electrode 14 and a hole transport layer (HTL) formed on the HIL.
  • the first sub-pixel 12A includes a first light-emitting layer 13A. In some embodiments, the first light-emitting layer 13A can be used to display green.
  • the organic material layer 18 is disposed on the electrode 14 and the pixel defining layer 16 in sections.
  • the first sub-pixel 12A and the second sub-pixel 12B respectively have different organic material layers 18 .
  • each sub-pixel includes an independent electrode 14 and an organic material layer 18 disposed on the electrode 14 .
  • operation 101 of method 100 includes forming a photoresist composition layer 22 on substrate 10 of the device.
  • Photoresist composition layer 22 includes a photoresist composition.
  • the photoresist composition includes a polymer polymerized by a first monomer and a second monomer, wherein the first monomer is an acrylic monomer containing a polymerizable group and a fluorine-containing group, and the second monomer is The monomer is a monomer containing a polymerizable group and a solubility-changing reactive group, a photobase generator, a thermal acid generator, and a first fluorinated solvent.
  • the photoresist composition is as described above and will not be described again here.
  • a sacrificial layer 21 is formed on the organic material layer 18 and the first light emitting layer 13A. In some embodiments, sacrificial layer 21 covers over organic material layer 18 . In some embodiments, the photoresist composition layer 22 is formed on the sacrificial layer 21 .
  • the sacrificial layer 21 can be disposed between the photoresist composition layer 22 and the substrate 10 .
  • the sacrificial layer 21 can be disposed between the photoresist composition layer 22 and the organic material layer 18 .
  • the sacrificial layer 21 can be used as a planarization layer to improve the flatness of the photoresist composition layer 22 or an adhesion layer to improve the bonding between the photoresist composition layer 22 and the organic material layer 18 .
  • a barrier layer (not shown in the figure) is further included between the sacrificial layer 21 and the photoresist composition layer 22 .
  • the etching rate of the barrier layer is different from that of the sacrificial layer 21 and the photoresist composition layer 22 . Therefore, highly selective etching can be performed without damaging the underlying material (sacrificial layer 21).
  • operation 102 of method 100 includes exposing photoresist composition layer 22 to patterned radiant energy to form exposed regions 23 and unexposed areas in photoresist composition layer 22 . Exposure area 24. In some embodiments, the photoresist composition layer 22 forms at least one exposed area 23 and at least one unexposed area 24 . In certain embodiments, the substrate 10 with the photoresist composition layer 22 is transferred to a photolithography exposure tool for an exposure process.
  • the exposure process is The photoresist composition layer 22 is exposed to radiant energy, such as deep ultraviolet light (DUV for short) or extreme ultraviolet light (EUV for short) through a photomask 25 with a pre-layout pattern, to obtain a plurality of exposure areas 23 and a plurality of The photoresist composition layer 22 in the unexposed area 24 .
  • radiant energy may be, for example, but not limited to, a 248 nm beam emitted by a krypton fluoride (KrF) excimer laser, or a 193 nm beam emitted by an argon fluoride (ArF) excimer laser.
  • the radiant energy may be, for example, but not limited to, EUV having a wavelength below about 13.5 nm.
  • the exposed areas of photoresist composition layer 22 are 23 Alkali is produced.
  • the thermal acid generator in photoresist composition layer 22 is unresponsive to radiant energy (light energy).
  • operation 103 of method 100 includes baking exposed areas 23 and unexposed areas 24 .
  • the substrate 10 having the photoresist composition layer 22 is subjected to a post-exposure bake process.
  • the exposed areas 23 and the unexposed areas of the photoresist composition layer 22 are heated by the thermal acid generator in the photoresist composition layer 22. 24 generates acid, and an acid-base neutralization reaction occurs with the alkali generated in the exposed area 23.
  • the unexposed area 24 can prevent the photoresist composition layer 22 from being dissolved in the developer under the condition that the thermal acid generator generates acid.
  • the temperature of the baked exposed area 23 and the unexposed area 24 is 90°C or less. In some embodiments, the temperature of baking the exposed area 23 and the unexposed area 24 is between 80 and 90°C.
  • operation 104 of method 100 includes removing exposed areas 23 of photoresist composition layer 22 to form developed structures 26 .
  • the photoresist composition layer 22 is subjected to a development process, for example but not limited to, the photoresist composition layer 22 is immersed in a developer (not shown in the figure) or the developer is coated on the photoresist layer 22 .
  • the photoresist composition layer 22 includes a positive photoresist, and the developer dissolves the exposed areas 23 .
  • the developer includes at least 50% by volume of a second fluorinated solvent.
  • the second fluorinated solvent and the first fluorinated solvent agents are the same or different.
  • the developer contains at least 90% by volume of one or more hydrofluoroether solvents.
  • the exposed portion of the sacrificial layer 21 from the developing structure 26 is removed, so that a portion of the organic material layer 18 is exposed from the sacrificial layer 21 .
  • the sacrificial layer 21 is patterned to form the recess 27.
  • the sacrificial layer 21 is patterned to form the recess 27 and further etched horizontally to form an undercut 28, such that More organic material layer 18 is exposed from sacrificial layer 21 .
  • the method 100 further includes forming a second light-emitting layer 13B above the photoresist composition layer 22 and on the second sub-pixel 12B through the recess 27 .
  • the second luminescent layer 13B may further cover the sidewalls of the recess 27 .
  • the method of forming the second light-emitting layer 13B can be the same as or different from that of forming the first light-emitting layer 13A, and can be through various deposition processes, such as but not limited to vapor deposition, sputtering, atomic layer deposition (ALD), Thermal evaporation, coating or jetting.
  • the second light-emitting layer 13B can be used to display an image of the second color. In some embodiments, the second light-emitting layer 13B can be used to display red color.
  • the method 100 further includes removing the photoresist composition layer 22 and the sacrificial layer 21 .
  • the photoresist composition layer 22 and the sacrificial layer 21 are removed using a stripping process.
  • sacrificial layer 21 is removed using a third fluorinated solvent.
  • the third fluorinated solvent is the same as or different from the second fluorinated solvent.
  • the third fluorinated solvent includes at least 90% by volume of one or more hydrofluoroether solvents.
  • a stripping process is used to remove the photoresist composition layer 22 and the sacrificial layer 21 while simultaneously removing the portion of the second light-emitting layer 13B located above the photoresist composition layer 22 .
  • the portion of the second light-emitting layer 13B located on the surface of the photoresist composition layer 22 is washed away together with the photoresist composition layer 22 , and the portion of the second light-emitting layer 13B located in the first concave portion 27 remains.
  • a pixel structure in which the first light-emitting layer 13A is located on the first sub-pixel 12A and the second light-emitting layer 13B is located on the second sub-pixel 12B can be formed.
  • the sequence of forming multiple light-emitting layers includes forming a first light-emitting layer 13A, then forming a second light-emitting layer 13B, and finally forming a third light-emitting layer (not shown in the figure) that displays a third color. But not limited to the above order.
  • the sequence of forming multiple light-emitting layers in this disclosure is designed to form more stable light-emitting layers first, and then form one or more less stable light-emitting layers, but is not limited to the above order. Other suitable sequences for forming the light emitting layer may also be used.
  • the word “simultaneously” refers to removing the second light-emitting layer 13B, the photoresist composition layer 22 and the second light-emitting layer 13B above the photoresist composition layer 22 in a single stripping process. part.
  • the sacrificial layer 21 and the portion of the second light-emitting layer 13B located above the photoresist composition layer 22 may be removed at different steps in the stripping process, but are not limited thereto.
  • the method 100 further includes forming a conductive layer 19 on the substrate 10 of the device.
  • the conductive layer 19 is formed on the organic material layer 18, the first luminescent layer 13A and the second luminescent layer 13B.
  • conductive layer 19 includes a transparent conductive material or an opaque conductive material.
  • conductive layer 19 includes magnesium.
  • Conductive layer 19 may include a similar conductive material as electrode 14 .
  • conductive layer 19 is designed to serve as the cathode of the device.
  • the conductive layer 19 can be connected to a driving circuit in the substrate 10 to receive a driving signal for driving the electroluminescent device.
  • the conductive layer 19 is continuously connected to the first sub-pixel 12A and the second sub-pixel 12B, but is not limited thereto.
  • the conductive layer 19 can be divided into several sections, wherein each section is vertically aligned with the first light-emitting layer 13A and the second light-emitting layer 13B respectively.
  • the second carrier transport layer and the second carrier injection layer can also be configured for each sub-pixel based on the above description, or shared with other sub-pixels, and the implementation shown in the figure It should not be considered as a limitation of the invention.
  • the method 100 further includes forming a second carrier transport layer and a second carrier injection layer between the first luminescent layer 13A and the second luminescent layer 13B and the conductive layer 19, or a combination of the foregoing.
  • the second carrier injection layer can be used for electron injection or hole injection.
  • the second carrier injection layer can be used for electron transport or hole transport.
  • the second carrier is an electron
  • the first light-emitting layer 13A An electron transport layer (ETL) is formed between the first luminescent layer 13A and the second luminescent layer 13B, and an electron injection layer (EIL) is formed between the ETL and the conductive layer 19.
  • ETL electron transport layer
  • EIL electron injection layer
  • a photoresist composition includes: a polymer polymerized from a first monomer and a second monomer, wherein the first monomer contains polymerizable An acrylic monomer with a group and a fluorine-containing group, the second monomer is a monomer containing a polymerizable group and a reactive group that can change the solubility; a photobase generator; a thermal acid generator; and monofluorinated solvents.
  • the polymer is formed by free radical polymerization of the first monomer and the second monomer, the first monomer is a monomer represented by formula (I), and the second monomer is The monomer is the monomer shown in formula (II):
  • R 1 represents a hydrogen atom, a cyano group, a methyl group or an ethyl group
  • R 2 represents a substituted or unsubstituted alkyl group having at least 5 fluorine atoms
  • R 3 represents a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms.
  • the alkyl group of R2 is a cyclic or acyclic hydrofluorocarbon or hydrofluoroether having at least as many fluorine atoms as carbon atoms.
  • the monomer represented by formula (II) is selected from the group consisting of: formula (II-1), formula (II-2), formula (II-3), formula (II) -4), or formula (II-5)
  • the thermal acid generator is selected from the group consisting of p-toluenesulfonic acid, dodecylbenzenesulfonic acid, fluorantibonic acid, triflate groups, and tris( Pentafluorophenyl)borane.
  • the photobase generator is selected from the group consisting of: formula (III-1), formula (III-2), formula (III-3), formula (III-4), Or formula (III-5):
  • a method of patterning a device includes forming a photoresist composition layer on a substrate of a device, the photoresist composition including a first unit A polymer formed by polymerizing a monomer and a second monomer, wherein the first monomer is an acrylic monomer containing a polymerizable group and a fluorine-containing group, and the second monomer is an acrylic monomer containing a polymerizable group.
  • a monomer with a solubility-modifying reactive group a photobase generator, a thermal acid generator, and a first fluorinated solvent
  • exposing the photoresist composition layer to patterned radiation to The photoresist composition layer forms an exposed area and an unexposed area; the exposed area and the unexposed area are baked; and the exposed area of the photoresist composition layer is removed to form a developed structure.
  • the device is an organic light emitting diode device
  • the substrate includes one or more layers of organic materials.
  • the exposed area is removed by contacting the exposed area with a developer including a second fluorinated solvent.
  • the content of the polymer ranges from 1 to 50wt%
  • the content of the photobase generator ranges from 0.1 to 20wt%
  • the thermal acid generator The content of the agent ranges from 0.1 to 20 wt%
  • the content of the fluorinated solvent ranges from 1 to 99 wt%.

Abstract

A photoresist composition, comprising: a polymer which is formed by polymerizing a first monomer and a second monomer, wherein the first monomer is an acrylic monomer containing a polymerizable group and a fluorine-containing atom group, and the second monomer is a monomer containing a polymerizable group and a reactive group capable of changing solubility; a photobase generator; a thermal acid generator; and a fluorinated solvent. A method for patterning a device, comprising: forming a photoresist composition layer (22) on a substrate (10) of a device, the photoresist composition layer (22) comprising a photoresist composition (S101); exposing the photoresist composition layer (22) to patterned radiation to form an exposed region (23) and an unexposed region (24) on the photoresist composition layer (22) (S102); baking the exposed region (23) and the unexposed region (24) (S103); and removing the exposed region (23) of the photoresist composition layer (22) to form a developed structure (26) (S104).

Description

一种光刻胶组成物及使装置图案化的方法Photoresist composition and method for patterning devices 技术领域Technical field
(相关申请案说明)本申请主张2022年04月18日提出的美国专利临时申请案第63/332,241号的优先权。此处将前述申请案的整体揭示内容纳入作为参照。(Description of related applications) This application claims priority to U.S. Patent Provisional Application No. 63/332,241 filed on April 18, 2022. The entire disclosure content of the aforementioned application is hereby incorporated by reference.
本揭示是关于一种光刻胶组成物及运用所述光刻胶组成物使装置图案化的方法。The present disclosure relates to a photoresist composition and a method of patterning a device using the photoresist composition.
背景技术Background technique
近年来对于显示器产业而言，有机发光二极体(organic light-emitting diode，OLED)装置是非常重要的技术，并已成为研究与发展的重点。OLED是一种光二极管light-emitting diode，LED)，其中有一层有机化合物薄膜置于两个导体间，并可回应譬如来自电流的刺激而发出光线。OLED可用于显示装置，譬如电视荧幕、电脑荧幕、行动电、平板电脑、智能手表与智能眼镜等应用。OLED装置是自发光装置，且因为其亮度、较佳的可视性以及相较于液晶装置有较佳的能显示较为清晰的影像而广受探讨。In recent years, organic light-emitting diode (OLED) devices are a very important technology for the display industry and have become the focus of research and development. OLED is a light-emitting diode (LED) in which a thin film of organic compounds is placed between two conductors and emits light in response to stimulation, such as from an electric current. OLED can be used in display devices, such as TV screens, computer screens, mobile phones, tablets, smart watches and smart glasses. OLED devices are self-illuminating devices and have been widely discussed due to their brightness, better visibility, and ability to display clearer images than LCD devices.
然而，当前OLED装置的制程发展遇到了瓶颈。主要的问题之一就是于制程中当多次的曝露于紫外光下容易导致OLED装置的组件效能下降。因此，如何能减少组件暴露于紫外光下是当前的研究方向之一。However, the current process development of OLED devices has encountered a bottleneck. One of the main problems is that repeated exposure to ultraviolet light during the manufacturing process can easily lead to a decrease in component performance of OLED devices. Therefore, how to reduce the exposure of components to ultraviolet light is one of the current research directions.
发明内容Contents of the invention
在本揭示中，一种光刻胶组成物，包含：一聚合物，由一第一单体及一第 二单体聚合而成，其中该第一单体为含可聚合基团与含氟原子基团的压克力单体，该第二单体为含可聚合基团与可改变溶解度反应性基团的单体；一光产碱剂；一热生酸剂；及一氟化溶剂。In this disclosure, a photoresist composition includes: a polymer composed of a first monomer and a first Polymerized from two monomers, the first monomer is an acrylic monomer containing a polymerizable group and a fluorine-containing group, and the second monomer is an acrylic monomer containing a polymerizable group and a reactive group that can change the solubility. A group of monomers; a photobase generator; a thermal acid generator; and a fluorinated solvent.
在本揭示中，一种使装置图案化的方法，包含：在一装置的一衬底上形成一光刻胶组成物层，该光刻胶组成物层包括一光刻胶组成物，该一光刻胶组成物包括由一第一单体及一第二单体聚合而成的一聚合物，其中该第一单体为含可聚合基团与含氟原子基团的压克力单体，该第二单体为含可聚合基团与可改变溶解度反应性基团的单体、一光产碱剂、一热生酸剂，及一第一氟化溶剂；暴露该光刻胶组成物层于经图案化的辐射，以在该光刻胶组成物层形成一曝光区及一未曝光区；烘烤该曝光区及该未曝光区；及移除该光刻胶组成物层的曝光区，形成一显影结构。In the present disclosure, a method of patterning a device includes forming a photoresist composition layer on a substrate of a device, the photoresist composition layer including a photoresist composition, the The photoresist composition includes a polymer polymerized from a first monomer and a second monomer, wherein the first monomer is an acrylic monomer containing a polymerizable group and a fluorine-containing group. , the second monomer is a monomer containing a polymerizable group and a solubility-changing reactive group, a photobase generator, a thermal acid generator, and a first fluorinated solvent; exposing the photoresist composition subjecting the photoresist composition layer to patterned radiation to form an exposed area and an unexposed area; baking the exposed area and the unexposed area; and removing the photoresist composition layer The exposure area forms a development structure.
附图说明Description of the drawings
为协助读者达到最佳理解效果，建议在阅读本揭示时同时参考附件图示及其详细说明。请注意为遵循业界标准做法，各种特征未依照比例绘制。事实上，为了清楚说明，各种特征的尺寸可能刻意放大或缩小。In order to help readers achieve the best understanding, it is recommended to refer to the attached illustrations and detailed descriptions when reading this disclosure. Please note that in compliance with industry standard practices, various features are not drawn to scale. In fact, the dimensions of various features may be intentionally exaggerated or reduced for clarity of illustration.
图1是根据本揭示的某些实施方式的使装置图案化的方法的流程图。Figure 1 is a flowchart of a method of patterning a device in accordance with certain embodiments of the present disclosure.
图2为根据本揭示内容某些实施方式的使装置图案化的方法的一装置的上视图。Figure 2 is a top view of a device according to a method of patterning a device in accordance with certain embodiments of the present disclosure.
图3至图10是根据本揭示的某些实施方式的各种阶段期间之一装置结构之剖面图。3-10 are cross-sectional views of a device structure during various stages according to certain embodiments of the present disclosure.
具体实施方式Detailed ways
以下揭示内容提供许多不同的实施例或范例，用于实施本申请案的不同特征。元件与配置的特定范例的描述如下，以简化本申请案的揭示内容。当然， 这些仅为范例，并非用于限制本申请案。The following disclosure provides many different embodiments or examples for implementing different features of the present application. Specific examples of components and configurations are described below to simplify the disclosure of this application. certainly, These are examples only and are not intended to limit this application.
OLED装置的一个关键挑战在于使红色、绿色、及蓝色像素的阵列图案化，且每一像素皆包含容易损坏且较为敏感的有机化合物材料，因此，本领域需要提出一种有效且不损伤OLED装置的使装置图案化的方法。A key challenge in OLED devices is to pattern arrays of red, green, and blue pixels, and each pixel contains easily damaged and sensitive organic compound materials. Therefore, the art needs to come up with an effective and non-damaging OLED A method of patterning a device.
在某些实施方式中，本揭示提出一种光刻胶组成物，包含：一聚合物，由一第一单体及一第二单体聚合而成，其中第一单体为含可聚合基团与含氟原子基团的压克力单体，第二单体为含可聚合基团与可改变溶解度反应性基团的单体；一光产碱剂(Photo base generator，简称PBG)；一热生酸剂(thermal acid generator，简称TAG)；及一氟化溶剂。在某些实施方式中，光刻胶组成物为正型光刻胶。In certain embodiments, the present disclosure provides a photoresist composition, including: a polymer polymerized from a first monomer and a second monomer, wherein the first monomer contains a polymerizable group An acrylic monomer with a group and a fluorine-containing group, the second monomer is a monomer containing a polymerizable group and a reactive group that can change the solubility; Photo base generator (PBG); A thermal acid generator (TAG); and a fluorinated solvent. In certain embodiments, the photoresist composition is a positive photoresist.
在某些实施方式中，聚合物由第一单体及第二单体进行自由基聚合反应而成，第一单体是如式(I)所示单体：
In some embodiments, the polymer is formed by free radical polymerization of a first monomer and a second monomer, and the first monomer is a monomer represented by formula (I):
在式(I)中，R1表示氢原子、氰基、甲基或乙基，R2表示具有至少5个氟原子的取代或未取代的烷基。在某些实施方式中，R2至少10个氟原子的取代或未取代的烷基。在某些实施方式中，R2的烷基为至少具有与碳原子一样多的氟原子的环状或非环状氢氟烃或者氢氟醚。在某些实施方式中，R2表示至少具有4个碳原子的全氟化烷基或1H，1H，2H，2H-全氟化烷基。在某些实施方式中，1H，1H，2H，2H-全氟化烷基可例如但不限于甲基丙烯酸1H,1H,2H,2H-全氟辛酯(简称FOMA)。在某些实施方式中，第一单体是如式(I-1)所示单体：
In formula (I), R 1 represents a hydrogen atom, a cyano group, a methyl group or an ethyl group, and R 2 represents a substituted or unsubstituted alkyl group having at least 5 fluorine atoms. In certain embodiments, R is a substituted or unsubstituted alkyl group of at least 10 fluorine atoms. In certain embodiments, the alkyl group of R2 is a cyclic or acyclic hydrofluorocarbon or hydrofluoroether having at least as many fluorine atoms as carbon atoms. In certain embodiments, R represents a perfluoroalkyl group having at least 4 carbon atoms or a 1H, 1H, 2H, 2H-perfluoroalkyl group. In certain embodiments, the 1H, 1H, 2H, 2H-perfluoroalkyl group may be, for example, but not limited to, 1H, 1H, 2H, 2H-perfluorooctyl methacrylate (FOMA for short). In certain embodiments, the first monomer is a monomer represented by formula (I-1):
在某些实施方式中，第二单体是如式(II)所示单体：
In certain embodiments, the second monomer is a monomer represented by formula (II):
在式(II)中，R3表示具有1至20个碳原子的直链、支化或环状烷基。在某些实施方式中，R3为叔烷基。在某些实施方式中，式(II)所示单体是选自由以下组成之群组：式(II-1)、式(II-2)、式(II-3)、式(II-4)，或式(II-5)In formula (II), R 3 represents a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms. In certain embodiments, R3 is tertiary alkyl. In certain embodiments, the monomer represented by formula (II) is selected from the group consisting of: formula (II-1), formula (II-2), formula (II-3), formula (II-4) ), or formula (II-5)
在某些实施方式中，第二单体是如式(II-2)所示单体。 In certain embodiments, the second monomer is a monomer represented by formula (II-2).
在某些实施方式中，聚合物是透过自由基聚合反应形成，可例如但不限于添加可进行热解产生自由基的热起始剂，于一定的聚合条件之下进行自由基聚合反应。在某些实施方式中，热起始剂可例如但不限于偶氮二异丁腈(2,2'-Azobis(isobutyronitrile)，简称AIBN)。In some embodiments, the polymer is formed through free radical polymerization. For example, but not limited to, adding a thermal initiator that can undergo pyrolysis to generate free radicals, and performing free radical polymerization under certain polymerization conditions. In certain embodiments, the thermal initiator may be, for example, but not limited to, 2,2'-Azobis (isobutyronitrile), AIBN for short.
在某些实施方式中，聚合物是透过式(I-1)所示单体与式(II-2)所示单体进行如下反应而成，使聚合物包含如下所示结构：
In some embodiments, the polymer is formed by reacting the monomer represented by formula (I-1) and the monomer represented by formula (II-2) as follows, so that the polymer contains the structure shown below:
在某些实施方式中，热生酸剂是选自由以下组成之群组：对甲苯磺酸(Para-Toluene-Sulfonic Acid，简称pTSA)、十二烷基苯磺酸(Dodecyl Benzene Sulfonic Acid，简称DDBSA)、氟锑酸(Fluoroantimonic acid，SbF6)、三氟甲磺酸酯基团(Triflate group，简称-OTf)，及三(五氟苯基)硼烷(Tris(pentafluorophenyl)borane，简称TPFB)。In some embodiments, the thermal acid generator is selected from the group consisting of: Para-Toluene-Sulfonic Acid (pTSA for short), Dodecyl Benzene Sulfonic Acid (Dodecyl Benzene Sulfonic Acid for short) DDBSA), Fluoroantimonic acid (SbF 6 ), Triflate group (-OTf), and Tris(pentafluorophenyl)borane (TPFB) ).
在某些实施方式中，光产碱剂是是选自由以下组成之群组：式(III-1)、式(III-2)、式(III-3)、式(III-4)，或式(III-5)

In certain embodiments, the photobase generator is selected from the group consisting of: formula (III-1), formula (III-2), formula (III-3), formula (III-4), or Formula (III-5)

在某些实施方式中，光刻胶组成物不包含光产酸剂。In certain embodiments, the photoresist composition does not include a photoacid generator.
在某些实施方式中，氟化溶剂包括室温下全氟化的或者高度氟化的溶剂，氟化溶剂与水和多数有机溶剂不相溶。氟化溶剂可例如但不限于高度环境友好且有“绿色”溶剂称号的氢氟醚(hydrofluoroether，简称HFE)。HFE(包括离析HFE)不可燃，具有零臭氧消耗潜能，且显示出对人体的毒性非常低。In certain embodiments, fluorinated solvents include room temperature perfluorinated or highly fluorinated solvents that are immiscible with water and most organic solvents. The fluorinated solvent may be, for example, but not limited to, hydrofluoroether (HFE), which is highly environmentally friendly and has the title of "green" solvent. HFE (including isolated HFE) is non-flammable, has zero ozone depletion potential, and has been shown to have very low toxicity to humans.
在某些实施方式中，HFE和HFE的同分异构混合物可例如但不限于甲基九氟丁基醚和甲基九氟异丁基醚的同分异构混合物(HFE-7100)、乙基九氟丁基醚和乙基九氟异丁基醚的同分异构混合物(HFE-7200aka NovecTM7200)、3-乙氧基-1,1,1,2,3,4,4,5,5,6,6,6-十二氟-2-三氟甲基-己烷(HFE-7500aka NovecTM7500)、1，1，1，2，3，3-六氟-4-(1,1,2,3,3,3-六氟丙氧基)-戊烷(HFE-7600aka NovecTM7600)、1-甲氧基七氟丙烷(HFE-7000)、1,1,1,2,2,3，4,5,5,5-十氟-3-甲氧基-4-三氟甲基戊烷(HFE-7300aka NovecTM7300)、1,3-(1，1,2,2-四氟乙氧基)苯(HFE-978m)、1,2-(1,1,2,2-四氟乙氧基)乙烷(HFE-578E)、1,1,2,2-四氟乙基-1H，1H，5H-八氟戊基醚(HFE-6512)、1,1,2,2-四氟乙基-2,2,2-三氟乙基醚(HFE-347E)、1,1,2,2-四气乙基-2,2,3,3-四气丙基酿(HFE-458E)、2,3,3,4,4-五气四氢-5-甲氧基-2,5-双[1,2,2,2-四氟-1-(三氟甲基)乙基]-呋喃(HFE-7700aka NovecTM7700)和1,1,1，2,2,3,3,4,4,5,5,6,6-十三氟辛烷-丙基醚(TE60-C3)。在某些实施方式中，光刻胶组成物还包含一醚类溶剂，可例如但不限于二乙二醇***(Diethylene glycol diethyl ether，简称DGDE)。In certain embodiments, HFE and isomeric mixtures of HFE may be, for example, but not limited to, methyl nonafluorobutyl ether and methyl nonafluoroisobutyl ether (HFE-7100), ethanol. Isomeric mixture of nonafluorobutyl ether and ethyl nonafluoroisobutyl ether (HFE-7200aka Novec TM 7200), 3-ethoxy-1,1,1,2,3,4,4, 5,5,6,6,6-dodecafluoro-2-trifluoromethyl-hexane (HFE-7500aka Novec TM 7500), 1,1,1,2,3,3-hexafluoro-4-( 1,1,2,3,3,3-Hexafluoropropoxy)-pentane (HFE-7600aka Novec TM 7600), 1-methoxyheptafluoropropane (HFE-7000), 1,1,1,2, 2,3,4,5,5,5-decafluoro-3-methoxy-4-trifluoromethylpentane (HFE-7300aka Novec TM 7300), 1,3-(1,1,2,2 -Tetrafluoroethoxy)benzene (HFE-978m), 1,2-(1,1,2,2-tetrafluoroethoxy)ethane (HFE-578E), 1,1,2,2-tetrafluoroethoxy) Fluoroethyl-1H, 1H, 5H-octafluoropentyl ether (HFE-6512), 1,1,2,2-tetrafluoroethyl-2,2,2-trifluoroethyl ether (HFE-347E) , 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl alcohol (HFE-458E), 2,3,3,4,4-pentafluorotetrahydro-5- Methoxy-2,5-bis[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]-furan (HFE-7700aka Novec TM 7700) and 1,1,1,2 ,2,3,3,4,4,5,5,6,6-tridecafluorooctane-propyl ether (TE60-C3). In some embodiments, the photoresist composition further includes an ether solvent, such as but not limited to diethylene glycol diethyl ether (DGDE).
在某些实施方式中，以光刻胶组成物重量为100wt％计，聚合物的含量范围 为1至50wt％、光产碱剂的含量范围为0.1至20wt％、热生酸剂的含量范围为0.1至20wt％，及氟化溶剂的含量范围为1至99wt％。In certain embodiments, based on 100 wt% of the photoresist composition, the content of the polymer ranges from The content of the photobase generator ranges from 1 to 50wt%, the content of the photobase generator ranges from 0.1 to 20wt%, the content of the thermal acid generator ranges from 0.1 to 20wt%, and the content of the fluorinated solvent ranges from 1 to 99wt%.
图1是根据本揭示的某些实施方式的使装置图案化的方法的流程图。如图1所示，方法100包含若干操作：(101)在一装置的一衬底上形成一光刻胶组成物层，光刻胶组成物层包括一光刻胶组成物，一光刻胶组成物包括由一第一单体及一第二单体聚合而成的一聚合物，其中第一单体为含可聚合基团与含氟原子基团的压克力单体，第二单体为含可聚合基团与可改变溶解度反应性基团的单体、一光产碱剂、一热生酸剂，及一第一氟化溶剂；(102)暴露光刻胶组成物层于经图案化的辐射，以在光刻胶组成物层形成一曝光区及一未曝光区；(103)烘烤曝光区及未曝光区；及(104)移除光刻胶组成物层的曝光区，形成一显影结构。Figure 1 is a flowchart of a method of patterning a device in accordance with certain embodiments of the present disclosure. As shown in Figure 1, the method 100 includes several operations: (101) Forming a photoresist composition layer on a substrate of a device, the photoresist composition layer includes a photoresist composition, a photoresist The composition includes a polymer polymerized from a first monomer and a second monomer, wherein the first monomer is an acrylic monomer containing a polymerizable group and a fluorine-containing group, and the second monomer The body is a monomer containing a polymerizable group and a solubility-changing reactive group, a photobase generator, a thermal acid generator, and a first fluorinated solvent; (102) Exposing the photoresist composition layer to Patterned radiation to form an exposed area and an unexposed area in the photoresist composition layer; (103) baking the exposed area and the unexposed area; and (104) removing the exposure of the photoresist composition layer area to form a developing structure.
图2为根据本揭示某些实施方式的使装置图案化的方法所处理的装置的上视图。如图2所示，提供衬底10。在某些实施方式中，方法100所处理的装置是一种电致发光装置。在某些实施方式中，方法100所处理的装置是OLED装置。Figure 2 is a top view of a device processed by a method of patterning a device in accordance with certain embodiments of the present disclosure. As shown in Figure 2, a substrate 10 is provided. In certain embodiments, the device processed by method 100 is an electroluminescent device. In some embodiments, the device processed by method 100 is an OLED device.
在某些实施方式中，装置的衬底10包括显示区域10D及周边区域10P。衬底10还包括位于显示区域10D中的复数个像素12。可将像素12排列为阵列。每一独立的像素12和其他相邻像素12分离。在某些实施方式中，每一像素12包括第一子像素12A及第二子像素12B。在某些实施方式中，每一像素12包括第一子像素12A、第二子像素12B及第三子像素12C。在某些实施方式中，子像素亦可称为子像素区或像素。In some embodiments, device substrate 10 includes display area 10D and peripheral area 10P. The substrate 10 also includes a plurality of pixels 12 located in the display area 10D. Pixels 12 may be arranged in an array. Each individual pixel 12 is separated from other adjacent pixels 12 . In some embodiments, each pixel 12 includes a first sub-pixel 12A and a second sub-pixel 12B. In some embodiments, each pixel 12 includes a first sub-pixel 12A, a second sub-pixel 12B, and a third sub-pixel 12C. In some embodiments, a sub-pixel may also be referred to as a sub-pixel region or pixel.
第一子像素12A、第二子像素12B及第三子像素12B可用以显示不同色彩。具体而言，第一子像素12A、第二子像素12B及第三子像素12C可分别用以发出第一色彩的影像、第二色彩的影像及第三色彩的影像。譬如，第一子像素12A可用以显示绿色、第二子像素12B可用以显示红色，且第三子像素12C可用以 显示蓝色。The first sub-pixel 12A, the second sub-pixel 12B and the third sub-pixel 12B can be used to display different colors. Specifically, the first sub-pixel 12A, the second sub-pixel 12B and the third sub-pixel 12C can respectively emit a first color image, a second color image and a third color image. For example, the first sub-pixel 12A can be used to display green, the second sub-pixel 12B can be used to display red, and the third sub-pixel 12C can be used to display red. Shows blue.
在某些实施方式中，子像素的排列包括，从左至右，第一子像素12A、第二子像素12B接着是第三子像素12C，但不限于此。亦可根据设计或其他考虑改变子像素的排置。再者，虽然图2绘示的子像素形状是方形，子像素也可采用其他形状。此外，像素12中的子像素数目可以是，但不限于，三个子像素；可改变子像素数目，且可使用其他适当的子像素来显示不同色彩，如黄色、白色或其他颜色。In some embodiments, the arrangement of the sub-pixels includes, from left to right, the first sub-pixel 12A, the second sub-pixel 12B and then the third sub-pixel 12C, but is not limited thereto. The arrangement of sub-pixels can also be changed based on design or other considerations. Furthermore, although the sub-pixel shape shown in FIG. 2 is square, the sub-pixels can also adopt other shapes. In addition, the number of sub-pixels in the pixel 12 may be, but is not limited to, three sub-pixels; the number of sub-pixels may be changed, and other appropriate sub-pixels may be used to display different colors, such as yellow, white or other colors.
在某些实施方式中，衬底10可以是硬式或可挠式衬底。此外，衬底10可以是不透明或透明衬底。衬底10可包括玻璃、石英、半导体材料(如硅、III-V族元素)或其他适当材料。在某些实施方式中，衬底10包括石墨烯。在某些实施方式中，可利用聚合物基质材料形成衬底10。衬底10上可选择性地设有介电层(图中未绘示)。在某些实施方式中，所述介电层可由氧化硅、氮化硅、氮氧化硅或其他适当材料制成。In certain embodiments, substrate 10 may be a rigid or flexible substrate. Furthermore, substrate 10 may be an opaque or transparent substrate. Substrate 10 may include glass, quartz, semiconductor materials (such as silicon, III-V elements), or other suitable materials. In certain embodiments, substrate 10 includes graphene. In certain embodiments, substrate 10 may be formed utilizing a polymeric matrix material. A dielectric layer (not shown in the figure) may optionally be provided on the substrate 10 . In certain embodiments, the dielectric layer may be made of silicon oxide, silicon nitride, silicon oxynitride, or other suitable materials.
图3至图10是根据本揭示的某些实施方式的各种阶段期间之一装置结构之剖面图。图3为沿着图2中A-A线段的像素的剖面示意图。在某些实施方式中，方法100是使用本揭示的光刻胶组成物。3-10 are cross-sectional views of a device structure during various stages according to certain embodiments of the present disclosure. FIG. 3 is a schematic cross-sectional view of a pixel along line segment A-A in FIG. 2 . In certain embodiments, method 100 uses the photoresist composition of the present disclosure.
在某些实施方式中，如图3所示，电极14形成于衬底10上。在某些实施方式中，复数个子像素共享一电极14。电极14可包括不透明导电材料或透明导电材料。不透明导电材料的实施例可包括金属，如铝(Al)、铜(Cu)、银(Ag)、金(Au)、钨(W)、另一种金属、或金属合金。透明导电材料的实施例可包括铟锡氧化物(indium tin oxide，简称ITO)、铟锌氧化物(indium zinc oxide，简称IZO)、铝掺杂锌氧化物(aluminum-doped zinc oxide，简称AZO)及铟掺杂镉氧化物，或其他类似材料。在某些实施方式中，电极14为装置的阳极。在某些实施方式中，复数个电极14彼此分离的形成于衬底10上，第一子像素12A、第二子像素12B分别具有不同的电极14。在某些实施方式中，每一子像 素包括一电极14。In certain embodiments, as shown in FIG. 3 , electrode 14 is formed on substrate 10 . In some embodiments, a plurality of sub-pixels share an electrode 14 . Electrode 14 may include opaque conductive material or transparent conductive material. Examples of opaque conductive materials may include a metal such as aluminum (Al), copper (Cu), silver (Ag), gold (Au), tungsten (W), another metal, or a metal alloy. Examples of transparent conductive materials may include indium tin oxide (ITO), indium zinc oxide (IZO), aluminum-doped zinc oxide (AZO) and indium-doped cadmium oxide, or other similar materials. In certain embodiments, electrode 14 is the anode of the device. In some embodiments, a plurality of electrodes 14 are formed separately on the substrate 10 , and the first sub-pixel 12A and the second sub-pixel 12B respectively have different electrodes 14 . In some embodiments, each sub-image The element includes an electrode 14.
在某些实施方式中，衬底10包括一驱动电路，譬如薄膜电晶体(thin film transistor，TFT)阵列。可依据所欲的像素排置来设计电极14的图样。电极14可电性连接至衬底10中的驱动电路，以接收用于驱动电致发光装置的驱动信号。In some embodiments, the substrate 10 includes a driving circuit, such as a thin film transistor (TFT) array. The pattern of the electrode 14 can be designed according to the desired pixel arrangement. The electrode 14 can be electrically connected to a driving circuit in the substrate 10 to receive a driving signal for driving the electroluminescent device.
虽然图3中仅绘示单一像素12中的第一子像素12A及第二子像素12B，本揭示的使装置图案化的方法可处理复数个像素12。Although only the first sub-pixel 12A and the second sub-pixel 12B in a single pixel 12 are shown in FIG. 3 , the disclosed method of patterning a device can process multiple pixels 12 .
在某些实施方式中，像素界定层(亦称为PDL)16形成在衬底10上，以分离第一子像素12A及第二子像素12B。在某些实施方式中，像素界定层16部分覆盖电极14并使电极14的一部分开放以供接收发光层。在另一些实施方式中(图中未绘示)，由装置的厚度方向观察，像素界定层16使多个电极14彼此分离。In some embodiments, a pixel defining layer (also referred to as PDL) 16 is formed on the substrate 10 to separate the first sub-pixel 12A and the second sub-pixel 12B. In certain embodiments, pixel defining layer 16 partially covers electrode 14 and leaves a portion of electrode 14 open to receive the light emitting layer. In other embodiments (not shown), the pixel defining layer 16 separates the plurality of electrodes 14 from each other when viewed through the thickness of the device.
像素界定层16可具有相同或不同形状。如图3所示，像素界定层16的剖面可具有弯曲表面。在某些实施方式中，像素界定层16的形状可为梯型、倒梯或方形。由装置的厚度方向观察，像素界定层16可排列于一格栅中。可依据所欲的像素排置来设计像素界定层16的图样。Pixel defining layers 16 may have the same or different shapes. As shown in FIG. 3 , the cross-section of the pixel defining layer 16 may have a curved surface. In some embodiments, the shape of the pixel defining layer 16 may be a trapezoid, an inverted ladder, or a square. Viewed through the thickness of the device, the pixel defining layers 16 may be arranged in a grid. The pattern of the pixel defining layer 16 can be designed according to the desired pixel arrangement.
在某些实施方式中，像素界定层16包括聚合物材料、感光材料或吸光材料，其颜色并没有特别限制。在某些实施方式中，透过一微影制程来形成像素界定层16。In some embodiments, the pixel defining layer 16 includes a polymer material, a photosensitive material or a light-absorbing material, and its color is not particularly limited. In some embodiments, the pixel defining layer 16 is formed through a photolithography process.
在某些实施方式中，在像素界定层16及经由像素界定层16暴露的电极14上形成一有机材料层18。有机材料层18为第一载子注入层、一第一载子传输层，或前述之一组合。第一载子注入层可用于空穴注入或电子注入。第一载子传输层可用于空穴传输或电子传输。在某些实施方式中，第一载子为空穴，有机材料层18包含一空穴注入层(HIL)形成于电极14上，以及一空穴传输层(HTL)形成于HIL上。在某些实施方式中，第一子像素12A包括一第一发光层13A。在某些实施方式中，第一发光层13A可用以显示绿色。 In some embodiments, an organic material layer 18 is formed over the pixel defining layer 16 and the electrode 14 exposed through the pixel defining layer 16 . The organic material layer 18 is a first carrier injection layer, a first carrier transport layer, or a combination of the above. The first carrier injection layer can be used for hole injection or electron injection. The first carrier transport layer can be used for hole transport or electron transport. In some embodiments, the first carriers are holes, and the organic material layer 18 includes a hole injection layer (HIL) formed on the electrode 14 and a hole transport layer (HTL) formed on the HIL. In some embodiments, the first sub-pixel 12A includes a first light-emitting layer 13A. In some embodiments, the first light-emitting layer 13A can be used to display green.
在另一些实施方式中(图中未绘示)，有机材料层18是分段地设置在电极14及像素界定层16上。在另一些实施方式中，第一子像素12A、第二子像素12B分别具有不同的有机材料层18。在另一些实施方式中，每一子像素包括各自独立的电极14及设置于电极14上的有机材料层18。In other embodiments (not shown in the figure), the organic material layer 18 is disposed on the electrode 14 and the pixel defining layer 16 in sections. In other embodiments, the first sub-pixel 12A and the second sub-pixel 12B respectively have different organic material layers 18 . In other embodiments, each sub-pixel includes an independent electrode 14 and an organic material layer 18 disposed on the electrode 14 .
在某些实施方式中，如图4所示，方法100的操作101包括在装置的衬底10上形成一光刻胶组成物层22。光刻胶组成物层22包括光刻胶组成物。光刻胶组成物包括由第一单体及第二单体聚合而成的一聚合物，其中第一单体为含可聚合基团与含氟原子基团的压克力单体，第二单体为含可聚合基团与可改变溶解度反应性基团的单体、光产碱剂、热生酸剂，及第一氟化溶剂。光刻胶组成物是如前所述，在此不再赘述。In some embodiments, as shown in FIG. 4 , operation 101 of method 100 includes forming a photoresist composition layer 22 on substrate 10 of the device. Photoresist composition layer 22 includes a photoresist composition. The photoresist composition includes a polymer polymerized by a first monomer and a second monomer, wherein the first monomer is an acrylic monomer containing a polymerizable group and a fluorine-containing group, and the second monomer is The monomer is a monomer containing a polymerizable group and a solubility-changing reactive group, a photobase generator, a thermal acid generator, and a first fluorinated solvent. The photoresist composition is as described above and will not be described again here.
在某些实施方式中，在有机材料层18上及第一发光层13A上形成牺牲层21。在某些实施方式中，牺牲层21覆盖有机材料层18上方。在某些实施方式中，光刻胶组成物层22形成于牺牲层21上。In some embodiments, a sacrificial layer 21 is formed on the organic material layer 18 and the first light emitting layer 13A. In some embodiments, sacrificial layer 21 covers over organic material layer 18 . In some embodiments, the photoresist composition layer 22 is formed on the sacrificial layer 21 .
牺牲层21可设于光刻胶组成物层22及衬底10间。牺牲层21可设于光刻胶组成物层22及有机材料层18间。牺牲层21可作为一平坦化层以提升光刻胶组成物层22的平整度或一黏着层以提升光刻胶组成物层22及有机材料层18间的接合。在另一些实施方式中，还包括一阻障层(图中未绘示)，位于牺牲层21及光刻胶组成物层22间。阻障层的蚀刻率和牺牲层21及光刻胶组成物层22不同。因此，可进行高选择性的蚀刻，而使得下方材料(牺牲层21)不会受损。The sacrificial layer 21 can be disposed between the photoresist composition layer 22 and the substrate 10 . The sacrificial layer 21 can be disposed between the photoresist composition layer 22 and the organic material layer 18 . The sacrificial layer 21 can be used as a planarization layer to improve the flatness of the photoresist composition layer 22 or an adhesion layer to improve the bonding between the photoresist composition layer 22 and the organic material layer 18 . In other embodiments, a barrier layer (not shown in the figure) is further included between the sacrificial layer 21 and the photoresist composition layer 22 . The etching rate of the barrier layer is different from that of the sacrificial layer 21 and the photoresist composition layer 22 . Therefore, highly selective etching can be performed without damaging the underlying material (sacrificial layer 21).
在某些实施方式中，如图5所示，方法100的操作102包括暴露光刻胶组成物层22于经图案化的辐射能，以在光刻胶组成物层22形成曝光区域23及未曝光区域24。在某些实施方式中，光刻胶组成物层22形成至少一曝光区域23及至少一未曝光区域24。在某些实施方式中，将具有光刻胶组成物层22的衬底10转移到光刻曝光工具进行曝光工艺。在某些实施方式中，曝光工艺是 通过具有预先布局图案的光掩模25将光刻胶组成物层22暴露于辐射能，诸如深紫外光(简称DUV)或极紫外光(简称EUV)，得到包括多个曝光区域23和多个未曝光区域24的光刻胶组成物层22。在某些实施方式中，辐射能可例如但不限于氟化氪(KrF)准分子激光器发射的248nm束，或由氟化氩(ArF)准分子激光器发射的193nm束。在某些实施方式中，辐射能可例如但不限于波长为约13.5nm以下的EUV。In certain embodiments, as shown in FIG. 5 , operation 102 of method 100 includes exposing photoresist composition layer 22 to patterned radiant energy to form exposed regions 23 and unexposed areas in photoresist composition layer 22 . Exposure area 24. In some embodiments, the photoresist composition layer 22 forms at least one exposed area 23 and at least one unexposed area 24 . In certain embodiments, the substrate 10 with the photoresist composition layer 22 is transferred to a photolithography exposure tool for an exposure process. In certain embodiments, the exposure process is The photoresist composition layer 22 is exposed to radiant energy, such as deep ultraviolet light (DUV for short) or extreme ultraviolet light (EUV for short) through a photomask 25 with a pre-layout pattern, to obtain a plurality of exposure areas 23 and a plurality of The photoresist composition layer 22 in the unexposed area 24 . In certain embodiments, the radiant energy may be, for example, but not limited to, a 248 nm beam emitted by a krypton fluoride (KrF) excimer laser, or a 193 nm beam emitted by an argon fluoride (ArF) excimer laser. In certain embodiments, the radiant energy may be, for example, but not limited to, EUV having a wavelength below about 13.5 nm.
在某些实施方式中，在暴露光刻胶组成物层22于经图案化的辐射能期间，通过光刻胶组成物层22中的光产碱剂，光刻胶组成物层22的曝光区域23有碱产生。在某些实施方式中，光刻胶组成物层22中的热生酸剂对辐射能(光能)没有反应。In certain embodiments, during exposure of photoresist composition layer 22 to patterned radiant energy, the exposed areas of photoresist composition layer 22 are 23 Alkali is produced. In certain embodiments, the thermal acid generator in photoresist composition layer 22 is unresponsive to radiant energy (light energy).
在某些实施方式中，如图6所示，方法100的操作103包括烘烤曝光区域23及未曝光区域24。在某些实施方式中，将具有光刻胶组成物层22的衬底10进行曝后烤工艺。在某些实施方式中，在烘烤曝光区域23及未曝光区域24期间，通过光刻胶组成物层22中的热生酸剂，光刻胶组成物层22的曝光区域23及未曝光区域24产生酸，与曝光区域23产生的碱发生酸碱中和反应。未曝光区域24在热生酸剂产生酸的条件下，可使光刻胶组成物层22不溶解于显影液。In some embodiments, as shown in FIG. 6 , operation 103 of method 100 includes baking exposed areas 23 and unexposed areas 24 . In some embodiments, the substrate 10 having the photoresist composition layer 22 is subjected to a post-exposure bake process. In some embodiments, during the baking of the exposed areas 23 and the unexposed areas 24, the exposed areas 23 and the unexposed areas of the photoresist composition layer 22 are heated by the thermal acid generator in the photoresist composition layer 22. 24 generates acid, and an acid-base neutralization reaction occurs with the alkali generated in the exposed area 23. The unexposed area 24 can prevent the photoresist composition layer 22 from being dissolved in the developer under the condition that the thermal acid generator generates acid.
在某些实施方式中，考虑第一发光层13A不耐100℃以上的高温，烘烤曝光区域23及未曝光区域24的温度是小于等于90℃。在某些实施方式中，烘烤曝光区域23及未曝光区域24的温度是介于80至90℃。In some embodiments, considering that the first light-emitting layer 13A is not resistant to high temperatures above 100°C, the temperature of the baked exposed area 23 and the unexposed area 24 is 90°C or less. In some embodiments, the temperature of baking the exposed area 23 and the unexposed area 24 is between 80 and 90°C.
在某些实施方式中，如图7所示，方法100的操作104包括移除光刻胶组成物层22的曝光区域23，形成显影结构26。在某些实施方式中，将光刻胶组成物层22进行显影工艺，可例如但不限于将光刻胶组成物层22浸入显影剂(图中未绘示)或将显影剂涂覆于光刻胶组成物层22。在某些实施方式中，光刻胶组成物层22包含正型光刻胶，显影剂将曝光区域23溶解。在某些实施方式中，显影剂包含按体积计至少50％的一第二氟化溶剂。第二氟化溶剂与第一氟化溶 剂相同或不同。在某些实施方式中，显影剂包含按体积计至少90％的一种或更多种氢氟醚溶剂。In certain embodiments, as shown in FIG. 7 , operation 104 of method 100 includes removing exposed areas 23 of photoresist composition layer 22 to form developed structures 26 . In some embodiments, the photoresist composition layer 22 is subjected to a development process, for example but not limited to, the photoresist composition layer 22 is immersed in a developer (not shown in the figure) or the developer is coated on the photoresist layer 22 . Resist composition layer 22. In some embodiments, the photoresist composition layer 22 includes a positive photoresist, and the developer dissolves the exposed areas 23 . In certain embodiments, the developer includes at least 50% by volume of a second fluorinated solvent. The second fluorinated solvent and the first fluorinated solvent agents are the same or different. In certain embodiments, the developer contains at least 90% by volume of one or more hydrofluoroether solvents.
在某些实施方式中，将牺牲层21自该显影结构26暴露的部分移除，使一部分的有机材料层18自牺牲层21露出。在某些实施方式中，牺牲层21经图样化以形成凹部27，在某些实施方式中，牺牲层21经图样化以形成凹部27还进一步被水平蚀刻而形成底切(undercut)28，使得更多的有机材料层18自牺牲层21露出。In some embodiments, the exposed portion of the sacrificial layer 21 from the developing structure 26 is removed, so that a portion of the organic material layer 18 is exposed from the sacrificial layer 21 . In some embodiments, the sacrificial layer 21 is patterned to form the recess 27. In some embodiments, the sacrificial layer 21 is patterned to form the recess 27 and further etched horizontally to form an undercut 28, such that More organic material layer 18 is exposed from sacrificial layer 21 .
在某些实施方式中，如图8所示，方法100还包括第二发光层13B形成于光刻胶组成物层22上方，并透过凹部27形成于第二子像素12B之上。在某些实施方式中(图中未绘示)，第二发光层13B可进一步覆盖凹部27的侧壁。形成第二发光层13B的方式可和形成第一发光层13A相同或不同，可藉由各种沉积制程，例如但不限于气相沉积、溅镀、原子层沉积(atomic layer deposition,简称ALD)、热蒸镀、涂覆或喷镀(jetting)。第二发光层13B可用以显示第二色彩的影像。在某些实施方式中，第二发光层13B可用以显示红色。In some embodiments, as shown in FIG. 8 , the method 100 further includes forming a second light-emitting layer 13B above the photoresist composition layer 22 and on the second sub-pixel 12B through the recess 27 . In some embodiments (not shown in the figure), the second luminescent layer 13B may further cover the sidewalls of the recess 27 . The method of forming the second light-emitting layer 13B can be the same as or different from that of forming the first light-emitting layer 13A, and can be through various deposition processes, such as but not limited to vapor deposition, sputtering, atomic layer deposition (ALD), Thermal evaporation, coating or jetting. The second light-emitting layer 13B can be used to display an image of the second color. In some embodiments, the second light-emitting layer 13B can be used to display red color.
在某些实施方式中，如图9所示，方法100还包括移除光刻胶组成物层22及牺牲层21。在某些实施方式中，光刻胶组成物层22及牺牲层21是利用剥除制程移除。在某些实施方式中，牺牲层21是利用第三氟化溶剂移除。第三氟化溶剂与第二氟化溶剂相同或不同。在某些实施方式中，第三氟化溶剂包含按体积计至少90％的一种或更多种氢氟醚溶剂。In some embodiments, as shown in FIG. 9 , the method 100 further includes removing the photoresist composition layer 22 and the sacrificial layer 21 . In some embodiments, the photoresist composition layer 22 and the sacrificial layer 21 are removed using a stripping process. In some embodiments, sacrificial layer 21 is removed using a third fluorinated solvent. The third fluorinated solvent is the same as or different from the second fluorinated solvent. In certain embodiments, the third fluorinated solvent includes at least 90% by volume of one or more hydrofluoroether solvents.
在某些实施方式中，利用剥除制程在移除光刻胶组成物层22及牺牲层21的同时，移除第二发光层13B位于光刻胶组成物层22上方的部分。换言之，连同光刻胶组成物层22一起洗除第二发光层13B位于光刻胶组成物层22的表面上的部分，第二发光层13B位于第凹部27中的部分仍然保留。如此一来，可形成第一发光层13A位于第一子像素12A上、第二发光层13B位于第二子像素12B上的像素结构。 In some embodiments, a stripping process is used to remove the photoresist composition layer 22 and the sacrificial layer 21 while simultaneously removing the portion of the second light-emitting layer 13B located above the photoresist composition layer 22 . In other words, the portion of the second light-emitting layer 13B located on the surface of the photoresist composition layer 22 is washed away together with the photoresist composition layer 22 , and the portion of the second light-emitting layer 13B located in the first concave portion 27 remains. In this way, a pixel structure in which the first light-emitting layer 13A is located on the first sub-pixel 12A and the second light-emitting layer 13B is located on the second sub-pixel 12B can be formed.
在某些实施方式中，形成多个发光层的顺序包括形成第一发光层13A，之后形成第二发光层13B，以及最后形成显示第三色彩的第三发光层(图中未绘示)，但不限于以上顺序。本揭示内容中形成多个发光层的顺序是经设计以便先形成较多稳定的发光层，其后形成较不稳定的一或多发光层，但不限于以上顺序。亦可采用其他形成发光层的适当顺序。In some embodiments, the sequence of forming multiple light-emitting layers includes forming a first light-emitting layer 13A, then forming a second light-emitting layer 13B, and finally forming a third light-emitting layer (not shown in the figure) that displays a third color. But not limited to the above order. The sequence of forming multiple light-emitting layers in this disclosure is designed to form more stable light-emitting layers first, and then form one or more less stable light-emitting layers, but is not limited to the above order. Other suitable sequences for forming the light emitting layer may also be used.
在本说明书中，「同时」一词是指在单一的剥除制程中，移除第二发光层13B、光刻胶组成物层22以及第二发光层13B位于光刻胶组成物层22上方的部分。在某些实施方式中，可在此剥除制程中的不同步骤移除牺牲层21以及第二发光层13B位于光刻胶组成物层22上方的部分，但不限于此。In this specification, the word "simultaneously" refers to removing the second light-emitting layer 13B, the photoresist composition layer 22 and the second light-emitting layer 13B above the photoresist composition layer 22 in a single stripping process. part. In some embodiments, the sacrificial layer 21 and the portion of the second light-emitting layer 13B located above the photoresist composition layer 22 may be removed at different steps in the stripping process, but are not limited thereto.
在另一些实施方式中(图中未绘示)，如图10所示，方法100还包括在装置的衬底10上形成导电层19。在某些实施方式中，导电层19是形成在有机材料层18、第一发光层13A及第二发光层13B上。在某些实施方式中，导电层19包括透明导电材料或不透明导电材料。在某些实施方式中，导电层19包括镁。导电层19可包括与电极14类似的导电材料。在某些实施方式中，导电层19经设计可作为装置的阴极。导电层19可用以连接至衬底10中的驱动电路，以接受用于驱动电致发光装置的驱动信号。In other embodiments (not shown), as shown in FIG. 10 , the method 100 further includes forming a conductive layer 19 on the substrate 10 of the device. In some embodiments, the conductive layer 19 is formed on the organic material layer 18, the first luminescent layer 13A and the second luminescent layer 13B. In certain embodiments, conductive layer 19 includes a transparent conductive material or an opaque conductive material. In certain embodiments, conductive layer 19 includes magnesium. Conductive layer 19 may include a similar conductive material as electrode 14 . In certain embodiments, conductive layer 19 is designed to serve as the cathode of the device. The conductive layer 19 can be connected to a driving circuit in the substrate 10 to receive a driving signal for driving the electroluminescent device.
在某些实施方式中，导电层19连续衬接于第一子像素12A、第二子像素12B，但不限于此。可将导电层19分为数个区段，其中每一区段分别与第一发光层13A及第二发光层13B垂直对齐。相似地，第二载子传输层及第二载子注入层亦可基于上文叙述针对每一子像素来配置每一层，或使其与其他子像素共享，且图中所示的实施方式不应视为对本发明的限制。In some embodiments, the conductive layer 19 is continuously connected to the first sub-pixel 12A and the second sub-pixel 12B, but is not limited thereto. The conductive layer 19 can be divided into several sections, wherein each section is vertically aligned with the first light-emitting layer 13A and the second light-emitting layer 13B respectively. Similarly, the second carrier transport layer and the second carrier injection layer can also be configured for each sub-pixel based on the above description, or shared with other sub-pixels, and the implementation shown in the figure It should not be considered as a limitation of the invention.
在某些实施方式中(图中未绘示)，方法100还包括在第一发光层13A及第二发光层13B与导电层19间形成第二载子传输层、第二载子注入层，或前述之一组合。第二载子注入层可用于电子注入或空穴注入。第二载子注入层可用于电子传输或空穴传输。在某些实施方式中，第二载子为电子，第一发光层13A 及第二发光层13B与导电层19间包含一电子传输层(ETL)形成于第一发光层13A及第二发光层13B上，以及电子注入层(EIL)形成于ETL与导电层19间。In some embodiments (not shown in the figure), the method 100 further includes forming a second carrier transport layer and a second carrier injection layer between the first luminescent layer 13A and the second luminescent layer 13B and the conductive layer 19, or a combination of the foregoing. The second carrier injection layer can be used for electron injection or hole injection. The second carrier injection layer can be used for electron transport or hole transport. In some embodiments, the second carrier is an electron, and the first light-emitting layer 13A An electron transport layer (ETL) is formed between the first luminescent layer 13A and the second luminescent layer 13B, and an electron injection layer (EIL) is formed between the ETL and the conductive layer 19.
于本揭示内容某些实施方式中,一种光刻胶组成物，包含：一聚合物，由一第一单体及一第二单体聚合而成，其中该第一单体为含可聚合基团与含氟原子基团的压克力单体，该第二单体为含可聚合基团与可改变溶解度反应性基团的单体；一光产碱剂；一热生酸剂；及一氟化溶剂。In certain embodiments of the present disclosure, a photoresist composition includes: a polymer polymerized from a first monomer and a second monomer, wherein the first monomer contains polymerizable An acrylic monomer with a group and a fluorine-containing group, the second monomer is a monomer containing a polymerizable group and a reactive group that can change the solubility; a photobase generator; a thermal acid generator; and monofluorinated solvents.
在某些实施方式中，其中该聚合物由该第一单体及该第二单体进行自由基聚合反应而成，该第一单体是如式(I)所示单体，该第二单体是如式(II)所示单体：
In some embodiments, the polymer is formed by free radical polymerization of the first monomer and the second monomer, the first monomer is a monomer represented by formula (I), and the second monomer is The monomer is the monomer shown in formula (II):
在该式(I)中，R1表示氢原子、氰基、甲基或乙基，R2表示具有至少5个氟原子的取代或未取代的烷基，在该式(II)中，R3表示具有1至20个碳原子的直链、支化或环状烷基。In the formula (I), R 1 represents a hydrogen atom, a cyano group, a methyl group or an ethyl group, R 2 represents a substituted or unsubstituted alkyl group having at least 5 fluorine atoms, and in the formula (II), R 3 represents a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms.
在某些实施方式中，在该式(I)中，R2的烷基为至少具有与碳原子一样多的氟原子的环状或非环状氢氟烃或者氢氟醚。In certain embodiments, in formula (I), the alkyl group of R2 is a cyclic or acyclic hydrofluorocarbon or hydrofluoroether having at least as many fluorine atoms as carbon atoms.
在某些实施方式中，其中该式(II)所示单体是选自由以下组成之群组：式(II-1)、式(II-2)、式(II-3)、式(II-4)，或式(II-5)
In certain embodiments, the monomer represented by formula (II) is selected from the group consisting of: formula (II-1), formula (II-2), formula (II-3), formula (II) -4), or formula (II-5)
在某些实施方式中，该热生酸剂是选自由以下组成之群组：对甲苯磺酸、十二烷基苯磺酸、氟锑酸、三氟甲磺酸酯基团，及三(五氟苯基)硼烷。In certain embodiments, the thermal acid generator is selected from the group consisting of p-toluenesulfonic acid, dodecylbenzenesulfonic acid, fluorantibonic acid, triflate groups, and tris( Pentafluorophenyl)borane.
在某些实施方式中，该光产碱剂是是选自由以下组成之群组：式(III-1)、式(III-2)、式(III-3)、式(III-4)，或式(III-5)：
In certain embodiments, the photobase generator is selected from the group consisting of: formula (III-1), formula (III-2), formula (III-3), formula (III-4), Or formula (III-5):
于本揭示内容某些实施方式中,一种使装置图案化的方法，包含：在一装置的一衬底上形成一光刻胶组成物层，该光刻胶组成物包括由一第一单体及一第二单体聚合而成的一聚合物，其中该第一单体为含可聚合基团与含氟原子基团的压克力单体，该第二单体为含可聚合基团与可改变溶解度反应性基团的单体、一光产碱剂、一热生酸剂，及一第一氟化溶剂；暴露该光刻胶组成物层于经图案化的辐射，以在该光刻胶组成物层形成一曝光区域及一未曝光区域；烘烤该曝光区域及该未曝光区域；及移除该光刻胶组成物层的该曝光区域，形成一显影结构。 In some embodiments of the present disclosure, a method of patterning a device includes forming a photoresist composition layer on a substrate of a device, the photoresist composition including a first unit A polymer formed by polymerizing a monomer and a second monomer, wherein the first monomer is an acrylic monomer containing a polymerizable group and a fluorine-containing group, and the second monomer is an acrylic monomer containing a polymerizable group. a monomer with a solubility-modifying reactive group, a photobase generator, a thermal acid generator, and a first fluorinated solvent; exposing the photoresist composition layer to patterned radiation to The photoresist composition layer forms an exposed area and an unexposed area; the exposed area and the unexposed area are baked; and the exposed area of the photoresist composition layer is removed to form a developed structure.
在某些实施方式中，该装置是一有机发光二极体装置，及该衬底包括一个或多个有机材料层。In certain embodiments, the device is an organic light emitting diode device, and the substrate includes one or more layers of organic materials.
在某些实施方式中，该曝光区域的移除是将该曝光区域与一显影剂接触，该显影剂包括一第二氟化溶剂。In certain embodiments, the exposed area is removed by contacting the exposed area with a developer including a second fluorinated solvent.
在某些实施方式中，以该光刻胶组成物重量为100wt％计，该聚合物的含量范围为1至50wt％、该光产碱剂的含量范围为0.1至20wt％、该热生酸剂的含量范围为0.1至20wt％，及该氟化溶剂的含量范围为1至99wt％。In some embodiments, based on the weight of the photoresist composition being 100wt%, the content of the polymer ranges from 1 to 50wt%, the content of the photobase generator ranges from 0.1 to 20wt%, and the thermal acid generator The content of the agent ranges from 0.1 to 20 wt%, and the content of the fluorinated solvent ranges from 1 to 99 wt%.
前述内容概述一些实施方式的特征，因而熟知此技艺的人士可更加理解本揭示的各方面。熟知此技艺的人士应理解可轻易使用本揭示作为基础，用于设计或修饰其他制程与结构而实现与本申请案所述的实施例具有相同目的与/或达到相同优点。熟知此技艺的人士亦应理解此均等架构并不脱离本揭示揭示内容的精神与范围，并且熟知此技艺的人士可进行各种变化、取代与替换，而不脱离本揭示的精神与范围。 The foregoing summary summarizes the features of some implementations so that those skilled in the art may better understand aspects of the present disclosure. Those skilled in the art should understand that the present disclosure can be readily used as a basis to design or modify other processes and structures to achieve the same purposes and/or achieve the same advantages as the embodiments described in this application. Those familiar with this art should also understand that this equal structure does not deviate from the spirit and scope of the disclosure, and those familiar with this art can make various changes, substitutions and substitutions without departing from the spirit and scope of this disclosure.

Claims (10)

  1. 一种光刻胶组成物，包含：A photoresist composition including:
    一聚合物，由一第一单体及一第二单体聚合而成，其中该第一单体为含可聚合基团与含氟原子基团的压克力单体，该第二单体为含可聚合基团与可改变溶解度反应性基团的单体；A polymer polymerized by a first monomer and a second monomer, wherein the first monomer is an acrylic monomer containing a polymerizable group and a fluorine-containing group, and the second monomer It is a monomer containing polymerizable groups and reactive groups that can change solubility;
    一光产碱剂；A photobase generator;
    一热生酸剂；及a thermal acid generator; and
    一氟化溶剂。Monofluorinated solvent.
  2. 如权利要求1所述的光刻胶组成物，其中该聚合物由该第一单体及该第二单体进行自由基聚合反应而成，该第一单体是如式(I)所示单体，该第二单体是如式(II)所示单体：
    The photoresist composition of claim 1, wherein the polymer is formed by free radical polymerization of the first monomer and the second monomer, and the first monomer is represented by formula (I) Monomer, the second monomer is a monomer shown in formula (II):
    在该式(I)中，R1表示氢原子、氰基、甲基或乙基，R2表示具有至少5个氟原子的取代或未取代的烷基，在该式(II)中，R3表示具有1至20个碳原子的直链、支化或环状烷基。In the formula (I), R 1 represents a hydrogen atom, a cyano group, a methyl group or an ethyl group, R 2 represents a substituted or unsubstituted alkyl group having at least 5 fluorine atoms, and in the formula (II), R 3 represents a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms.
  3. 如权利要求2所述的光刻胶组成物，其中在该式(I)中，R2的烷基为至少具有与碳原子一样多的氟原子的环状或非环状氢氟烃或者氢氟醚。The photoresist composition of claim 2, wherein in the formula (I), the alkyl group of R2 is a cyclic or acyclic hydrofluorocarbon or hydrogen having at least as many fluorine atoms as carbon atoms. Fluorine.
  4. 如权利要求2所述的光刻胶组成物，其中该式(II)所示单体是选自由以下组成之群组：式(II-1)、式(II-2)、式(II-3)、式(II-4)，或式(II-5)

    The photoresist composition of claim 2, wherein the monomer represented by formula (II) is selected from the group consisting of: formula (II-1), formula (II-2), formula (II- 3), formula (II-4), or formula (II-5)

  5. 如权利要求1所述的光刻胶组成物，其中该热生酸剂是选自由以下组成之群组：对甲苯磺酸、十二烷基苯磺酸、氟锑酸、三氟甲磺酸酯基团，及三(五氟苯基)硼烷。The photoresist composition of claim 1, wherein the thermal acid generator is selected from the group consisting of p-toluenesulfonic acid, dodecylbenzenesulfonic acid, fluorantibonic acid, and trifluoromethanesulfonic acid. ester group, and tris(pentafluorophenyl)borane.
  6. 如权利要求1所述的光刻胶组成物，其中该光产碱剂是选自由以下组成之群组：式(III-1)、式(III-2)、式(III-3)、式(III-4)，或式(III-5)
    The photoresist composition of claim 1, wherein the photobase generator is selected from the group consisting of: formula (III-1), formula (III-2), formula (III-3), formula (III-4), or formula (III-5)
  7. 一种使装置图案化的方法，包含：A method of patterning a device consisting of:
    在一装置的一衬底上形成一光刻胶组成物层，该光刻胶组成物包括由一第 一单体及一第二单体聚合而成的一聚合物，其中该第一单体为含可聚合基团与含氟原子基团的压克力单体，该第二单体为含可聚合基团与可改变溶解度反应性基团的单体、一光产碱剂、一热生酸剂，及一第一氟化溶剂；Forming a photoresist composition layer on a substrate of a device, the photoresist composition including a first A polymer formed by polymerizing a monomer and a second monomer, wherein the first monomer is an acrylic monomer containing a polymerizable group and a fluorine-containing group, and the second monomer is an acrylic monomer containing a polymerizable group. Monomers with polymeric groups and reactive groups that can change solubility, a photobase generator, a thermal acid generator, and a first fluorinated solvent;
    暴露该光刻胶组成物层于经图案化的辐射，以在该光刻胶组成物层形成一曝光区域及一未曝光区域；Exposing the photoresist composition layer to patterned radiation to form an exposed area and an unexposed area in the photoresist composition layer;
    烘烤该曝光区域及该未曝光区域；及Bake the exposed area and the unexposed area; and
    移除该光刻胶组成物层的该曝光区域，形成一显影结构。The exposed area of the photoresist composition layer is removed to form a developed structure.
  8. 权利要求7所述的方法，其中该装置是一有机发光二极体装置，及该衬底包括一个或多个有机材料层。7. The method of claim 7, wherein the device is an organic light emitting diode device and the substrate includes one or more layers of organic materials.
  9. 权利要求7所述的方法，其中该曝光区域的移除是将该曝光区域与一显影剂接触，该显影剂包括一第二氟化溶剂。7. The method of claim 7, wherein the removal of the exposed area is by contacting the exposed area with a developer, the developer including a second fluorinated solvent.
  10. 权利要求7所述的方法，其中以该光刻胶组成物重量为100wt％计，该聚合物的含量范围为1至50wt％、该光产碱剂的含量范围为0.1至20wt％、该热生酸剂的含量范围为0.1至20wt％，及该氟化溶剂的含量范围为1至99wt％。 The method of claim 7, wherein based on the weight of the photoresist composition being 100wt%, the content of the polymer ranges from 1 to 50wt%, the content of the photobase generator ranges from 0.1 to 20wt%, and the thermal The content of the acid generator ranges from 0.1 to 20 wt%, and the content of the fluorinated solvent ranges from 1 to 99 wt%.
PCT/CN2023/086787 2022-04-18 2023-04-07 Photoresist composition and method for patterning device WO2023202390A1 (en)

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