WO2016201823A1 - 亲水光刻胶、量子点层图案化的方法及量子点发光二极管 - Google Patents

亲水光刻胶、量子点层图案化的方法及量子点发光二极管 Download PDF

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WO2016201823A1
WO2016201823A1 PCT/CN2015/091031 CN2015091031W WO2016201823A1 WO 2016201823 A1 WO2016201823 A1 WO 2016201823A1 CN 2015091031 W CN2015091031 W CN 2015091031W WO 2016201823 A1 WO2016201823 A1 WO 2016201823A1
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photoresist
quantum dot
hydrophilic
group
dot layer
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PCT/CN2015/091031
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English (en)
French (fr)
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张斌
周婷婷
张锋
张伟
高锦成
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京东方科技集团股份有限公司
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Priority to US15/313,910 priority Critical patent/US10386724B2/en
Publication of WO2016201823A1 publication Critical patent/WO2016201823A1/zh

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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/02Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies
    • H01L33/04Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies with a quantum effect structure or superlattice, e.g. tunnel junction
    • H01L33/06Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies with a quantum effect structure or superlattice, e.g. tunnel junction within the light emitting region, e.g. quantum confinement structure or tunnel barrier

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  • Embodiments of the present invention relate to a hydrophilic photoresist, a quantum dot layer patterning method, and a quantum dot light emitting diode (QLED), a quantum dot color film, and a display device.
  • QLED quantum dot light emitting diode
  • Quantum Dot also known as nanocrystal, is a nanoparticle composed of II-VI or III-V elements. Since electrons and holes are quantum confined, continuous band structure changes. It is a discrete energy level structure with molecular characteristics. It can emit fluorescence after being excited. Its luminescence spectrum can be controlled by changing the size of quantum dots. The fluorescence intensity and stability are very good. It is a good electroluminescent material. .
  • quantum dots have been widely used as display materials in the field of display, for example, quantum dot light-emitting diodes fabricated using quantum dots as luminescent materials for luminescent layers.
  • Embodiments of the present invention provide a method of quantum dot layer patterning in response to the problem of prior art patterned methods of destroying quantum dots.
  • a method of quantum dot layer patterning comprising the steps of:
  • a step of forming a photoresist material layer on the substrate a step of patterning the photoresist, and a step of performing hydrophilic treatment on the photoresist;
  • the step of stripping the photoresist The step of stripping the photoresist.
  • the step of forming a photoresist material layer on the substrate, the step of patterning the photoresist, and the step of performing hydrophilic treatment on the photoresist do not limit the order;
  • the step of subjecting the photoresist to hydrophilic treatment may be performed before patterning after forming a photoresist material layer on the substrate, or after forming a photoresist material layer and patterning.
  • the step of forming a photoresist material layer on the substrate, the step of patterning the photoresist, and the step of hydrophilically treating the photoresist together form a hydrophilic photoresist pattern.
  • the pattern of the hydrophilic photoresist just exposes the area on the substrate where the quantum dots need to be coated.
  • the step of performing a hydrophilic treatment on the photoresist is performed before the step of forming a layer of the photoresist material; the step of forming a layer of the photoresist material on the substrate and pro-contacting the photoresist
  • the steps of water treatment include:
  • Patterning is performed after the above-described hydrophilic photoresist material layer is formed on the substrate.
  • the hydrophilic photoresist has a hydrophilic dialdehyde content of from 1 to 20% by weight.
  • the step of performing a hydrophilic treatment on the photoresist is performed after the step of forming a layer of the photoresist material; and the step of performing the hydrophilic treatment on the photoresist comprises:
  • the substrate is heated and the surface of the photoresist forms a hydrophilic group.
  • the acid is selected from one or more of oxalic acid, maleic acid, maleic anhydride, acetic acid, trichloroacetic acid, benzenesulfonic acid, tartaric acid, citric acid, racemic malic acid.
  • the hydrophilic dialdehyde aqueous solution has a mass concentration of 3 to 20% and a pH of 2 to 5.5.
  • the soaking time is between 5 and 30 minutes.
  • the heating the substrate comprises: heating at a temperature of 90 to 160 ° C for 5 to 60 minutes.
  • the hydrophilic dialdehyde structure is:
  • R is a hydrophilic group
  • n 1 is 0 or a positive integer
  • n 2 is a positive integer
  • n 3 is 0 or a positive integer
  • n 4 is a positive integer
  • (n 1 +n 2 +n 3 )*n 4 3 ⁇ 10.
  • the hydrophilic group comprises one or more of a carboxyl group, a carboxyl salt, a hydroxyl group, an amino group, a quaternary ammonium salt, an ester group, a hydrazide group, an amide group, or a sulfonic acid group.
  • the photoresist comprises a phenolic resin.
  • the step of forming a layer of photoresist material on the substrate further comprises the step of performing quantum dot anchoring force treatment on the substrate.
  • the quantum dot anchoring force treatment increases the adhesion of the substrate to the quantum dots.
  • Embodiments of the present invention provide a method for preparing a hydrophilic dialdehyde, which is a synthesis of 2-ethanol-hexanedialdehyde: using 3-cyclohexene-1-methanol (CAS: 1679-51-2) as a raw material.
  • the three-step reaction produces hydrophilic dialdehyde 2-ethanol-hexanedialdehyde.
  • the reaction process is as follows:
  • hydrophilic dialdehyde The above method for preparing a hydrophilic dialdehyde is merely an example, and those skilled in the art can empirically prepare other hydrophilic group-containing hydrophilic dialdehydes by using other similar raw materials.
  • Embodiments of the present invention also provide a photoresist for quantum dot patterning, the photoresist containing a hydrophilic group.
  • Embodiments of the present invention also provide a quantum dot light emitting diode (QLED) comprising a light emitting layer comprising the quantum dot layer prepared by the patterning method described above.
  • QLED quantum dot light emitting diode
  • Embodiments of the present invention also provide a quantum dot color film comprising the quantum dot layer prepared by the above-described patterning method.
  • Embodiments of the present invention also provide a display device comprising the QLED or quantum dot color film described above.
  • the method of quantum dot layer patterning of the embodiment of the present invention comprises the step of hydrophilically treating the photoresist, which can improve the hydrophilic property of the photoresist, and the quantum dots are in the photoresist due to the lipophilicity of the quantum dots.
  • the adhesion on the top is extremely low.
  • the quantum dot patterning method of an embodiment of the present invention is applicable to including quantum dots Light-emitting diodes.
  • FIG. 1 is a schematic diagram showing the steps of a conventional quantum dot layer patterning method.
  • FIG. 2 is a schematic view showing the steps of a method of patterning a quantum dot layer according to Embodiment 2 of the present invention.
  • FIG. 3 is a schematic diagram showing the steps of another method of quantum dot layer patterning according to Embodiment 2 of the present invention.
  • FIG. 4 is a schematic view showing the structure of a quantum dot according to Embodiment 2 of the present invention.
  • reference numerals have the following meanings: 1. a substrate; 2. a photoresist; 3. a quantum dot; 31, a luminescent core; 32, a semiconductor shell; 33, an organic ligand.
  • the substrate 1 shows a quantum dot patterning method comprising coating a photoresist 2 on a substrate 1 and exposing it, and then coating an entire layer of quantum dots 3 on the substrate 1, wherein the substrate 1 is lithographically free.
  • the quantum dot 3 at the glue 2 is required to be retained. Since the bonding force of the quantum dot 3 and the photoresist 2 is strong, if the quantum dot 3 on the photoresist 2 is directly cleaned at this time, the substrate 1 is also washed away without the photoresist 2; It is a complete layer. If the photoresist 2 is directly stripped at this time, the photoresist 2 is under the quantum dot 3 and cannot be brought into contact with the stripping liquid, and the stripping is not possible.
  • hydrophilic treatment refers to treating the contact angle of the photoresist with water to be less than 40°.
  • the hydrophilically treated photoresist has a contact angle to water of less than or equal to 35°.
  • quantum dots when a substance is modified by "hydrophobic” or “lipophilic”, it means that the contact angle of the substance described with water is greater than 40°.
  • quantum dots have a contact angle with water of greater than 40 due to the presence of lipophilic groups (or hydrophobic groups) on the surface.
  • the quantum dots have a contact angle with water of greater than or equal to 45°.
  • hydrophilic photoresist pattern means that the surface of the photoresist pattern is hydrophilic.
  • the surface of the photoresist pattern is hydrophilic so that the adhesion between the quantum dots having hydrophobicity (or lipophilicity) on the surface and the photoresist is low, and it is relatively easy to remove quantum dots on the surface of the photoresist pattern.
  • Embodiment 1 A method of quantum dot layer patterning, comprising the steps of:
  • Forming a hydrophilic photoresist pattern including:
  • the photoresist pattern is stripped.
  • the forming a hydrophilic photoresist pattern includes:
  • the layer of hydrophilic photoresist material is then patterned to form a photoresist pattern.
  • the hydrophilic treatment of the photoresist includes:
  • the substrate is heated and the surface of the layer of photoresist material forms a hydrophilic group.
  • the method of patterning a quantum dot layer according to embodiment 4, wherein the heating the substrate comprises: heating at a temperature of 90 to 160 ° C for 5 to 60 minutes. For example, it is heated at a temperature of 90 to 100 ° C for 5 to 60 minutes.
  • R is a hydrophilic group
  • n 1 is 0 or a positive integer
  • n 2 is a positive integer
  • n 3 is 0 or a positive integer
  • n 4 is a positive integer
  • (n 1 +n 2 +n 3 )*n 4 3 ⁇ 10.
  • hydrophilic group is selected from the group consisting of a carboxyl group, a carboxyl salt, a hydroxyl group, an amino group, a quaternary ammonium salt, and an ester group. And a hydrazide group, an amide group, and a sulfonic acid group.
  • Performing quantum dot anchoring treatment on the substrate includes treating the substrate with a silane coupling agent.
  • a silane coupling agent is a type of organosilicon compound containing two different chemical groups in a molecule, which can be represented by the formula YSiX 3 .
  • Y is a non-hydrolyzable group, including an alkenyl group (e.g., a vinyl group), and a functional group having a terminal such as Cl, NH 2 , SH, an epoxy, N 3 , a (meth)acryloyloxy group, or an isocyanate group; a hydrocarbon group, that is, a carbon functional group;
  • X is a hydrolyzable group, including Cl, OMe, OEt, OC 2 H 4 OCH 3 , OSiMe 3 and OAc, and the like.
  • the silane coupling agent has a reactive group capable of chemically bonding with an inorganic material (such as glass, silica sand, metal, etc.) and a reactive group chemically bonded to an organic material (synthetic resin or the like) in its molecule, it can be used. For surface treatment.
  • an inorganic material such as glass, silica sand, metal, etc.
  • an organic material synthetic resin or the like
  • the silane coupling agent When the silane coupling agent is used for treatment, the silane coupling agent is formulated into a dilute solution having a concentration of 0.5 to 1%, and only a thin solution of a silane coupling agent is applied to the cleaned surface to be used after drying. You can apply the glue.
  • the solvent used may be water, alcohol (methanol selected for methoxysilane, ethanol selected from ethoxysilane), or a mixture of hydroalcohols. In some embodiments, the solvent used is selected from the group consisting of water without fluoride ions, inexpensive non-toxic ethanol, and isopropanol.
  • the silane coupling agent does not contain an aminoalkylsilane, the solution prepared from the silane coupling agent needs to be added with acetic acid as a hydrolysis catalyst to adjust the pH to 3.5 to 5.5.
  • An exemplary method of quantum dot anchoring treatment involves placing the substrate in hexamethyldisilazane (HMDS) vapor, heating to 100-180 ° C, placing it for 20-120 min, and then taking it out for cooling.
  • HMDS hexamethyldisilazane
  • Embodiment 13 The method of quantum dot layer patterning according to embodiment 1, wherein the photoresist pattern just exposes a region on the substrate where quantum dots need to be coated.
  • Embodiment 14 A photoresist for quantum dot layer patterning, wherein the photoresist contains a hydrophilic group, wherein the hydrophilic group is derived from a hydrophilic dialdehyde.
  • Embodiment 15 The photoresist for quantum dot layer patterning of Embodiment 14, wherein the structural formula of the hydrophilic dialdehyde is:
  • R is a hydrophilic group
  • n 1 is 0 or a positive integer
  • n 2 is a positive integer
  • n 3 is 0 or a positive integer
  • n 4 is a positive integer
  • (n 1 +n 2 +n 3 )*n 4 3 ⁇ 10.
  • Embodiment 16 The photoresist for quantum dot layer patterning of Embodiment 14 or 15, wherein the hydrophilic group is selected from the group consisting of a carboxyl group, a carboxyl salt, a hydroxyl group, an amino group, a quaternary ammonium salt, an ester group, a hydrazide group, Amido group, and sulfonic acid group.
  • the hydrophilic group is selected from the group consisting of a carboxyl group, a carboxyl salt, a hydroxyl group, an amino group, a quaternary ammonium salt, an ester group, a hydrazide group, Amido group, and sulfonic acid group.
  • Embodiment 17 A quantum dot light emitting diode (QLED) comprising a light emitting layer, wherein the light emitting layer comprises the quantum dot layer prepared by the method of quantum dot layer patterning according to any one of embodiments 1-13.
  • QLED quantum dot light emitting diode
  • Embodiment 18 A quantum dot color film comprising the quantum dot according to any one of embodiments 1-13 A quantum dot layer prepared by a layer patterning method.
  • Embodiment 19 A display device comprising the QLED described in Embodiment 17 or the quantum dot color film described in Embodiment 18.
  • This embodiment provides a method for quantum dot layer patterning, including the following steps:
  • a step of forming a photoresist material layer on the substrate by using a photoresist a step of patterning the photoresist material layer to form a photoresist pattern, and a step of performing hydrophilic treatment on the photoresist;
  • the step of stripping the photoresist pattern is the step of stripping the photoresist pattern.
  • the steps are not limited;
  • the step of subjecting the photoresist to a hydrophilic treatment may be performed before patterning after forming the photoresist material layer, or after forming a photoresist material layer and patterning.
  • the method for patterning a quantum dot layer of the present embodiment includes the step of performing a hydrophilic treatment on the photoresist, so that the hydrophilicity of the photoresist can be improved, and since the quantum dots are lipophilic (or hydrophobic), The adhesion of the quantum dots to the photoresist is extremely low.
  • the photoresist is stripped, the quantum dots on the target position of the substrate are not peeled off.
  • the target position refers to a region on the substrate where quantum dots need to be coated.
  • the method of quantum dot patterning of embodiments of the present invention is applicable to light emitting diodes including quantum dots.
  • This embodiment provides a method for patterning a quantum dot layer, as shown in FIG. 2-4, including the following steps:
  • the photoresist 2 is subjected to a hydrophilic treatment to improve the hydrophilic property of the photoresist 2.
  • the quantum dot 3 includes three portions, namely a luminescent core 31, a semiconductor shell 32, and an organic ligand 33.
  • the quantum dot patterning method of an embodiment of the present invention is suitable for preparing a light emitting diode display including quantum dots.
  • the step of performing a hydrophilic treatment on the photoresist 2 is performed after the step of forming a material layer of the photoresist 2; the step of performing the hydrophilic treatment on the photoresist 2 includes:
  • the substrate 1 is heated, and the surface of the photoresist 2 layer forms a hydrophilic group.
  • the surface of the photoresist 2 can be modified only to modify the surface of the photoresist 2 to be hydrophilic, so as to reduce the quantum dot 3 on the photoresist 2. Adhesion.
  • the patterning method is an example of exposure and development.
  • the photoresist 2 may be subjected to hydrophilic treatment, then exposed and developed to form a hydrophilic photoresist pattern, coated with quantum dots 3, and then washed.
  • the quantum dots 3 remaining on the surface of the photoresist 2 are removed, and finally the photoresist 2 is stripped.
  • the photoresist 2 is exposed, developed, and then subjected to a hydrophilic treatment, and the quantum dots 3 are coated, and the quantum dots 3 remaining on the surface of the photoresist 2 are washed away, and finally the photolithography is performed.
  • Glue 2 is an example of exposure and development.
  • the photoresist 2 may be subjected to hydrophilic treatment, then exposed and developed to form a hydrophilic photoresist pattern, coated with quantum dots 3, and then washed.
  • the quantum dots 3 remaining on the surface of the photoresist 2 are removed, and finally the photoresist 2 is stripped.
  • the acid is selected from one or more of the group consisting of oxalic acid, maleic acid, maleic anhydride, acetic acid, trichloroacetic acid, benzenesulfonic acid, tartaric acid, citric acid, and racemic malic acid.
  • hydrophilic dialdehyde aqueous solution can be prepared by using any of the above acids.
  • the hydrophilic dialdehyde aqueous solution has a mass concentration of 3 to 20% and a pH of 2 to 5.5.
  • the aqueous hydrophilic dialdehyde solution is adjusted with an acid to a mass concentration of 3 to 20% and a pH of 2 to 5.5.
  • the soaking time is between 5 and 30 minutes.
  • heating the substrate comprises: heating at a temperature of 90 to 160 ° C for 5 to 60 minutes.
  • heating at a temperature of 90 to 160 ° C for 5 to 60 minutes allows the surface of the photoresist 2 to sufficiently react with the aqueous solution of the hydrophilic dialdehyde.
  • the hydrophilic dialdehyde structure is:
  • R is a hydrophilic group
  • n 1 is 0 or a positive integer
  • n 2 is a positive integer
  • n 3 is 0 or a positive integer
  • n 4 is a positive integer
  • (n 1 +n 2 +n 3 )*n 4 3 ⁇ 10.
  • Embodiments of the present invention provide a method for preparing a hydrophilic dialdehyde, which is a synthesis of 2-ethanol-hexanedialdehyde: using 3-cyclohexene-1-methanol (CAS: 1679-51-2) as a raw material.
  • the three-step reaction produces hydrophilic dialdehyde 2-ethanol-hexanedialdehyde.
  • the reaction process is as follows:
  • the hydrophilic group includes one or more of a carboxyl group, a carboxyl salt, a hydroxyl group, an amino group, a quaternary ammonium salt, an ester group, a hydrazide group, an amide group, or a sulfonic acid group.
  • the photoresist comprises a phenolic resin.
  • a linear phenol resin is reacted with a hydrophilic dialdehyde to form a bulk phenol resin, and a hydrophilic group is introduced into the phenol resin.
  • the step of forming a layer of photoresist 2 material on the substrate 1 further includes the step of performing quantum dot anchoring treatment on the substrate 1.
  • the substrate is subjected to quantum dot 3 anchoring treatment before the photoresist 2 is coated on the board 1.
  • the step of performing hydrophilic treatment on the photoresist 2 may also be performed before the step of forming a material layer of the photoresist 2;
  • the step of forming a layer of the photoresist 2 material and the step of performing the hydrophilic treatment on the photoresist 2 include:
  • the photoresist 2 is mixed with a hydrophilic dialdehyde to obtain a hydrophilic photoresist containing a hydrophilic group;
  • hydrophilic photoresist 2 material layer is formed on the substrate 1.
  • the photoresist 2 can be modified into a photoresist 2 containing a hydrophilic group to reduce the adhesion of the quantum dots 3 on the photoresist 2.
  • the hydrophilic photoresist has a hydrophilic dialdehyde content of from 1 to 20% by weight.
  • the hydrophilic dialdehyde content is 1 to 20% by weight.
  • the present embodiment provides a photoresist for quantum dot layer patterning, the photoresist containing a hydrophilic group, wherein the hydrophilic group is derived from a hydrophilic dialdehyde.
  • the structural formula of the hydrophilic dialdehyde is:
  • R is a hydrophilic group
  • n 1 is 0 or a positive integer
  • n 2 is a positive integer
  • n 3 is 0 or a positive integer
  • n 4 is a positive integer
  • (n 1 +n 2 +n 3 )*n 4 3 ⁇ 10.
  • the hydrophilic group is selected from the group consisting of a carboxyl group, a carboxyl salt, a hydroxyl group, an amino group, a quaternary ammonium salt, an ester group, a hydrazide group, an amide group, and a sulfonic acid group.
  • the dialdehyde is 2-ethanol-hexanedialdehyde.
  • 2-ethanol-hexanedialdehyde was synthesized by the following method: 3-cyclohexene-1-methanol (CAS: 1679-51-2) was used as a raw material to form a hydrophilic dialdehyde 2-ethanol-hexane after three steps of reaction.
  • Aldehyde the reaction process is as follows:
  • This embodiment provides a QLED comprising the quantum dot layer prepared by the patterning method described in Example 2.
  • the QLED further includes a cathode, an anode, and an electron injection layer, an electron transport layer, a hole blocking layer, a hole transport layer, and a hole injection layer between the cathode and the anode; the pattern described in Embodiment 2
  • the quantum dot prepared by the method is provided as a light-emitting layer between the hole blocking layer and the hole transport layer.
  • the present embodiment provides a quantum dot color film comprising the quantum dot layer prepared by the patterning method of Embodiment 2.
  • the embodiment provides a display device including the QLED of Embodiment 4 or the quantum dot color film of Embodiment 5.

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Abstract

提供一种光刻胶、量子点层图案化的方法及QLED、量子点彩膜和显示装置,其可解决现有的图案化的方法破坏量子点的问题。量子点层图案化的方法包括以下步骤:形成亲水光刻胶图案,包括:用光刻胶在基板(1)上形成光刻胶(2)材料层,对光刻胶(2)材料层进行构图从而形成光刻胶图案,和对光刻胶进行亲水处理;涂布量子点(3);除去保留在光刻胶图案上的量子点;和剥离光刻胶图案。量子点层图案化的方法可以提高光刻胶的亲水性能,降低具有亲油性的量子点在光刻胶上的附着力。

Description

亲水光刻胶、量子点层图案化的方法及量子点发光二极管 技术领域
本发明的实施例涉及一种亲水光刻胶、量子点层图案化的方法及量子点发光二极管(QLED)、量子点彩膜和显示装置。
背景技术
量子点(Quantum Dot,QD)又可称为纳米晶,是一种由II-VI族或III-V族元素组成的纳米颗粒,由于电子和空穴被量子限域,连续的能带结构变成具有分子特性的分立能级结构,受激后可以发射荧光,其发光光谱可以通过改变量子点的尺寸大小来控制,荧光强度和稳定性都很好,是一种很好的电致发光材料。
目前,量子点作为一种显示材料已经被广泛使用在了显示领域,例如,利用量子点作为发光材料用于发光层制造出的量子点发光二极管。
发明人发现现有技术中至少存在如下问题:由于量子点并不是小分子有机材料,因此目前没有适合量产的量子点图案化手段。
同时,也无法通过蒸镀方式和喷墨方式进行图案化;目前行业普遍接受的方法是转印法,但该方法很不成熟,工艺难度极大,目前均未量产,另外转印设备的供应商也很少,因此制约了QLED的发展。
发明内容
本发明的实施例针对现有的图案化的方法破坏量子点的问题,提供一种量子点层图案化的方法。
解决该问题所采用的技术方案是:
一种量子点层图案化的方法,包括以下步骤:
在基板上形成光刻胶材料层的步骤,对光刻胶进行构图的步骤,对光刻胶进行亲水处理的步骤;
涂布量子点的步骤;
除去剩余在(保留在)光刻胶上的量子点的步骤;
剥离光刻胶的步骤。
其中,在基板上形成光刻胶材料层的步骤,对光刻胶进行构图的步骤,对光刻胶进行亲水处理的步骤,不限定先后顺序;
对光刻胶进行亲水处理的步骤可以在在基板上形成光刻胶材料层之后构图之前进行,也可以在形成光刻胶材料层并构图之后进行。
在基板上形成光刻胶材料层的步骤,对光刻胶进行构图的步骤,和对光刻胶进行亲水处理的步骤一起形成亲水光刻胶图案。该亲水光刻胶的图案在基板上恰好暴露出需要涂覆量子点的区域。
在一些实施方式中,所述对光刻胶进行亲水处理的步骤在形成光刻胶材料层的步骤之前进行;所述在基板上形成光刻胶材料层的步骤和对光刻胶进行亲水处理的步骤包括:
将光刻胶与亲水性二醛混合得到含有亲水基团的亲水性光刻胶;
在基板上形成上述亲水性光刻胶材料层之后进行构图。
在一些实施方式中,所述亲水性光刻胶中亲水性二醛含量为1-20wt%。
在一些实施方式中,所述对光刻胶进行亲水处理的步骤在形成光刻胶材料层的步骤之后进行;对光刻胶进行亲水处理的步骤包括:
配制含酸的亲水性二醛水溶液,所述亲水性二醛中含有亲水基团;
将形成光刻胶材料层的基板浸泡于上述水溶液中;
将基板加热,光刻胶表面形成亲水基团。
在一些实施方式中,所述酸选自草酸、马来酸、马来酸酐、乙酸、三氯乙酸、苯磺酸、酒石酸、柠檬酸、消旋苹果酸中的一种或几种。
在一些实施方式中,所述亲水性二醛水溶液质量浓度为3~20%、pH为2~5.5。
在一些实施方式中,所述浸泡的时间为5~30min。
在一些实施方式中,所述将基板加热包括:在90~160℃的温度下加热5~60min。
在一些实施方式中,所述亲水性二醛结构式为:
Figure PCTCN2015091031-appb-000001
其中R为亲水基团,n1为0或正整数,n2为正整数,n3为0或正整数,n4为正整数,并且(n1+n2+n3)*n4=3~10。
在一些实施方式中,所述亲水基团包括羧基、羧盐、羟基、氨基、季铵盐、酯基、酰肼基、酰胺基或磺酸基中的一种或几种。
在一些实施方式中,所述光刻胶包括酚醛树脂。
在一些实施方式中,在基板上形成光刻胶材料层的步骤之前还包括:对所述基板进行量子点锚定力处理的步骤。所述量子点锚定力处理提高基板对量子点的粘着力。
本发明的实施例提供一种亲水性二醛的制备方法,2-乙醇-己二醛的合成:以3-环己烯-1-甲醇(CAS:1679-51-2)为原料,经过三步反应生成亲水性二醛2-乙醇-己二醛,反应过程如下:
Figure PCTCN2015091031-appb-000002
上述制备亲水性二醛的方法仅为举例,本领域技术人员可以根据经验,采用其它相类似的原料制备出上述含有亲水基团的亲水性二醛。
本发明的实施例还提供一种量子点图案化用光刻胶,所述光刻胶含有亲水基团。
本发明的实施例还提供一种量子点发光二极管(QLED),包括发光层,所述发光层包括上述的图案化的方法制备的量子点层。
本发明的实施例还提供一种量子点彩膜,所述量子点彩膜包括上述的图案化的方法制备的量子点层。
本发明的实施例还提供一种显示装置,包括上述的QLED或量子点彩膜。
本发明的实施例的量子点层图案化的方法包括对光刻胶进行亲水处理的步骤,这样可以提高光刻胶的亲水性能,由于量子点具有亲油性,使得量子点在光刻胶上的附着力极低。在剥离光刻胶的时候,不会造成基板目标位置上的量子点脱落。本发明的实施例的量子点图案化的方法适用于包括量子点 的发光二极管。
附图说明
为了更清楚地说明本发明实施例的技术方案,下面将对实施例的附图作简单地介绍,显而易见地,下面描述中的附图仅仅涉及本发明的一些实施例,而非对本发明的限制。
图1为现有的量子点层图案化的方法的步骤示意图。
图2为本发明的实施例2的量子点层图案化的方法的步骤示意图。
图3为本发明的实施例2的另一种量子点层图案化的方法的步骤示意图。
图4为本发明的实施例2的量子点结构示意图。
在附图中,附图标记具有以下含义:1、基板;2、光刻胶;3、量子点;31、发光核;32、半导体壳;33、有机配体。
具体实施方式
为使本发明实施例的目的、技术方案和优点更加清楚,下面将结合本发明实施例的附图,对本发明实施例的技术方案进行清楚、完整地描述。显然,所描述的实施例是本发明的一部分实施例,而不是全部的实施例。基于所描述的本发明的实施例,本领域普通技术人员在无需创造性劳动的前提下所获得的所有其他实施例,都属于本发明保护的范围。
图1示出了一种量子点图案化方法,包括在基板1上涂布光刻胶2并曝光后,再在上述基板1上涂布整层的量子点3,其中基板1的无光刻胶2处的量子点3是需要保留的。由于量子点3与光刻胶2的结合力较强,故此时如果直接清洗光刻胶2上的量子点3,则基板1无光刻胶2处的也被洗掉;又由于量子点3是完整的层,如果此时直接剥离光刻胶2,则光刻胶2在量子点3之下,无法与剥离液接触,剥离不了。
在本申请中,当某一物质用“亲水的”来修饰时,是指所描述的物质与水的接触角小于40°。例如,在本申请中,亲水处理是指将光刻胶与水的接触角处理为小于40°。在一些实施方式中,亲水处理的光刻胶与水的接触角为小于或等于35°。
在本申请中,当某一物质用“疏水的”或者“亲油的”来修饰时,是指所描述的物质与水的接触角大于40°。例如,在本申请中,量子点由于表面上带有亲油基团(或者疏水基团),与水的接触角大于40°。在一些实施方式中,量子点与水的接触角为大于或等于45°。
在本申请中,术语“亲水光刻胶图案”是指光刻胶图案的表面具有亲水性。光刻胶图案的表面具有亲水性使得表面具有疏水性(或亲油性)的量子点与光刻胶之间的附着力低,比较容易除去光刻胶图案的表面上的量子点。
本申请提供以下实施方式:
实施方式1.一种量子点层图案化的方法,包括以下步骤:
形成亲水光刻胶图案,包括:
用光刻胶在基板上形成光刻胶材料层,
对光刻胶材料层进行构图从而形成光刻胶图案,和
对光刻胶进行亲水处理;
涂布量子点;
除去保留在光刻胶图案上的量子点;和
剥离光刻胶图案。
实施方式2.根据实施方式1所述的量子点层图案化的方法,其中,
所述对光刻胶进行亲水处理在所述形成光刻胶材料层之前进行;
所述的形成亲水光刻胶图案包括:
将光刻胶与亲水性二醛混合得到含有亲水基团的亲水性光刻胶;
在基板上形成所述亲水性光刻胶材料层;和
然后对所述亲水性光刻胶材料层进行构图从而形成光刻胶图案。
实施方式3.根据实施方式2所述的量子点层图案化的方法,其中,所述亲水性光刻胶中亲水性二醛含量为1-20wt%。
实施方式4.根据实施方式1所述的量子点层图案化的方法,其中,
所述对光刻胶进行亲水处理在形成光刻胶材料层之后进行;
所述对光刻胶进行亲水处理包括:
配制含酸的亲水性二醛水溶液,所述亲水性二醛中含有亲水基团;
将形成光刻胶材料层的基板浸泡于所述水溶液中;
将基板加热,光刻胶材料层的表面形成亲水基团。
实施方式5.根据实施方式4所述的量子点层图案化的方法,其中,所述酸选自草酸、马来酸、马来酸酐、乙酸、三氯乙酸、苯磺酸、酒石酸、柠檬酸、和消旋苹果酸。
实施方式6.根据实施方式4或5所述的量子点层图案化的方法,其中,所述亲水性二醛水溶液的质量浓度为3~20wt%、pH为2~5.5。
实施方式7.根据实施方式4-6中任一项所述的量子点层图案化的方法,其中,所述浸泡的时间为5~30min。
实施方式8.根据实施方式4所述的量子点层图案化的方法,其中,所述将基板加热包括:在90~160℃的温度下加热5~60min。例如,在90~100℃的温度下加热5~60min。
实施方式9.根据实施方式2或4所述的量子点层图案化的方法,其中,所述亲水性二醛结构式为:
Figure PCTCN2015091031-appb-000003
其中R为亲水基团,n1为0或正整数,n2为正整数,n3为0或正整数,n4为正整数,并且(n1+n2+n3)*n4=3~10。
实施方式10.根据实施方式2-9中任一项所述的量子点层图案化的方法,其中,所述亲水基团选自羧基、羧盐、羟基、氨基、季铵盐、酯基、酰肼基、酰胺基、和磺酸基。
实施方式11.根据实施方式1-10中任一项所述的量子点层图案化的方法,其中,所述光刻胶包括酚醛树脂。
实施方式12.根据实施方式1所述的量子点层图案化的方法,其中所述方法还包括,在形成所述光刻胶材料层之前,对所述基板进行量子点锚定力处理。
对所述基板进行量子点锚定力处理包括用硅烷偶联剂对基板进行处理。
硅烷偶联剂是一类在分子中同时含有两种不同化学性质基团的有机硅化合物,其可用通式YSiX3表示。式中,Y为非水解基团,包括链烯基(如乙烯基),以及末端带有Cl、NH2、SH、环氧、N3、(甲基)丙烯酰氧基、异氰酸 酯基等官能团的烃基,即碳官能基;X为可水解基团,包括Cl、OMe、OEt、OC2H4OCH3、OSiMe3及OAc等。因为硅烷偶联剂在其分子中同时具有能和无机质材料(如玻璃、硅砂、金属等)化学结合的反应基团及与有机质材料(合成树脂等)化学结合的反应基团,所以可以用于表面处理。
在用硅烷偶联剂进行处理时,将硅烷偶联剂配成0.5~1%浓度的稀溶液,使用时只需在清洁的被粘表面涂上一层硅烷偶联剂的稀溶液,干燥后即可上胶。所用溶剂可为水、醇(甲氧基硅烷选择甲醇,乙氧基硅烷选择乙醇)、或水醇混合物。在一些实施方式中,所用的溶剂选自不含氟离子的水、价廉无毒的乙醇、和异丙醇。当所述硅烷偶联剂不包含氨烃基硅烷时,由硅烷偶联剂配制的溶液均需加入醋酸作水解催化剂,将pH值调至3.5~5.5。
一种示例性的量子点锚定力处理的方法包括将基板置于六甲基二硅胺(HMDS)蒸汽中,加热至100-180℃,放置20-120min,然后取出冷却。
实施方式13.根据实施方式1所述的量子点层图案化的方法,其中,所述光刻胶图案恰好暴露出基板上需要涂覆量子点的区域。
实施方式14.一种量子点层图案化用光刻胶,其中,所述光刻胶含有亲水基团,其中所述亲水基团源自亲水性二醛。
实施方式15.实施方式14的量子点层图案化用光刻胶,其中,所述亲水性二醛的结构式为:
Figure PCTCN2015091031-appb-000004
其中R为亲水基团,n1为0或正整数,n2为正整数,n3为0或正整数,n4为正整数,并且(n1+n2+n3)*n4=3~10。
实施方式16.实施方式14或15的量子点层图案化用光刻胶,其中,所述亲水基团选自羧基、羧盐、羟基、氨基、季铵盐、酯基、酰肼基、酰胺基、和磺酸基。
实施方式17.一种量子点发光二极管(QLED),包括发光层,其中,所述发光层包括实施方式1-13任一项所述的量子点层图案化的方法制备的量子点层。
实施方式18.一种量子点彩膜,包括实施方式1-13任一项所述的量子点 层图案化的方法制备的量子点层。
实施方式19.一种显示装置,包括实施方式17中所述的QLED或实施方式18中所述的量子点彩膜。
实施例
以下将结合附图对本申请的具体实施例进行描述。
实施例1:
本实施例提供一种量子点层图案化的方法,包括以下步骤:
用光刻胶在基板上形成光刻胶材料层的步骤,对光刻胶材料层进行构图从而形成光刻胶图案的步骤,对光刻胶进行亲水处理的步骤;
涂布量子点的步骤;
除去保留在光刻胶图案上的量子点的步骤;
剥离光刻胶图案的步骤。
其中,在基板上形成光刻胶材料层的步骤,对光刻胶进行构图的步骤,对光刻胶进行亲水处理的步骤,步骤不限定先后顺序;
对光刻胶进行亲水处理的步骤可以在形成光刻胶材料层之后构图之前进行,也可以在形成光刻胶材料层并构图之后进行。
本实施例的量子点层图案化的方法中,包括对光刻胶进行亲水处理的步骤,这样可以提高光刻胶的亲水性,由于量子点具有亲油性(或者说是疏水性),使得量子点在光刻胶上的附着力极低。在剥离光刻胶的时候,不会造成基板目标位置上的量子点脱落。所述的目标位置是指基板上需要涂覆量子点的区域。本发明的实施例的量子点图案化的方法适用于包括量子点的发光二极管。
实施例2:
本实施例提供一种量子点层图案化的方法,如图2-4所示,包括以下步骤:
在基板1上形成光刻胶2材料层的步骤,对光刻胶2进行构图从而形成光刻胶图案的步骤,对光刻胶2进行亲水处理的步骤;
涂布量子点3的步骤;
除去保留在光刻胶图案上的量子点的步骤;
剥离光刻胶2的步骤。
也就是说,本实施例将光刻胶2进行亲水处理,以提高光刻胶2的亲水性能。
量子点3的结构示意图如图4所示,量子点3包括三个部分,分别是发光核31,半导体壳32,有机配体33;所述有机配体33包括亲油基团,如源自油胺CH3(CH2)7CH=CH(CH2)7CH2NH2,或油酸CH3(CH2)7CH=CH(CH2)7COOH的基团。由于量子点3具有亲油性,使得量子点3在光刻胶2上的附着力极低。在除去光刻胶图案上的量子点以及剥离光刻胶2的时候,不会造成基板1目标位置上的量子点3脱落。本发明的实施例的量子点图案化的方法适用于制备包括量子点的发光二极管显示器。
在一些示例中,所述对光刻胶2进行亲水处理的步骤在形成光刻胶2材料层的步骤之后进行;对光刻胶2进行亲水处理的步骤包括:
配制含酸的亲水性二醛水溶液,亲水性二醛中含有亲水基团;
将形成光刻胶2材料层的基板1浸泡于上述含酸的亲水性二醛水溶液中;
将基板1加热,光刻胶2层表面形成亲水基团。
也就是说,作为本实施例的一种实施方式,可以仅在光刻胶2表面做改性,将光刻胶2表面改性为亲水性,以降低量子点3在光刻胶2上的附着力。
其中,构图方式以曝光、显影为例,可以如图2所示,先对光刻胶2进行亲水处理,然后再曝光、显影形成亲水光刻胶图案,涂布量子点3,再洗去保留在光刻胶2表面的量子点3,最后剥离光刻胶2。也可以如图3所示,先将光刻胶2曝光、显影,然后再进行亲水处理,涂布量子点3,再洗去保留在光刻胶2表面的量子点3,最后剥离光刻胶2。
在一些实施方式中,酸选自草酸、马来酸、马来酸酐、乙酸、三氯乙酸、苯磺酸、酒石酸、柠檬酸、消旋苹果酸中的一种或几种。
也就是说,采用上述任意酸配制亲水性二醛水溶液即可。
在一些实施方式中,亲水性二醛水溶液质量浓度为3~20%、pH为2~5.5。
也就是说,采用酸将亲水性二醛水溶液调节至其质量浓度为3~20%、pH为2~5.5。
在一些实施方式中,浸泡的时间为5~30min。
也就是说,浸泡5~30min,即可保证表面的光刻胶与亲水性二醛水溶液充分接触。
在一些实施方式中,将基板加热包括:在90~160℃的温度下加热5~60min。
也就是说,在90~160℃的温度下加热5~60min,使得表面的光刻胶2与亲水性二醛水溶液充分反应。
在一些实施方式中,亲水性二醛结构式为:
Figure PCTCN2015091031-appb-000005
其中R为亲水基团,n1为0或正整数,n2为正整数,n3为0或正整数,n4为正整数,并且(n1+n2+n3)*n4=3~10。
本发明的实施例提供一种亲水性二醛的制备方法,2-乙醇-己二醛的合成:以3-环己烯-1-甲醇(CAS:1679-51-2)为原料,经过三步反应生成亲水性二醛2-乙醇-己二醛,反应过程如下:
Figure PCTCN2015091031-appb-000006
在一些实施方式中,亲水基团包括羧基、羧盐、羟基、氨基、季铵盐、酯基、酰肼基、酰胺基或磺酸基中的一种或几种。
也就是说,本领域技术人员可以根据经验掌握选取不同的原料,带有上述的亲水基团以合成上述的亲水性二醛。
在一些实施方式中,光刻胶包括酚醛树脂。
也就是说,采用线型的酚醛树脂与亲水性二醛反应生成体型的酚醛树脂,在酚醛树脂中引入亲水基团。
在一些实施方式中,在基板1上形成光刻胶2材料层的步骤之前还包括:对基板1进行量子点锚定力处理的步骤。
也就是说,为了增加基板1目标位置上的量子点3的附着力,可以在基 板1上涂覆光刻胶2之前对基板进行量子点3锚定力处理。
在一些实施方式中,作为本实施例的另一种方式,所述对光刻胶2进行亲水处理的步骤也可以在形成光刻胶2材料层的步骤之前进行;所述在基板1上形成光刻胶2材料层的步骤和对光刻胶2进行亲水处理的步骤包括:
将光刻胶2与亲水性二醛混合得到含有亲水基团的亲水性光刻胶;
在基板1上形成上述亲水性光刻胶2材料层。
也就是说,可以将光刻胶2改性为含有亲水基团的光刻胶2,以降低量子点3在光刻胶2上的附着力。
在一些实施方式中,亲水性光刻胶中亲水性二醛含量为1-20wt%。
也就是说,将光刻胶2与亲水性二醛混合后的混合液中,亲水性二醛含量为1-20wt%。
实施例3:
本实施例提供一种量子点层图案化用光刻胶,所述光刻胶含有亲水基团,其中所述亲水基团源自亲水性二醛。
在一些示例中,所述亲水性二醛的结构式为:
Figure PCTCN2015091031-appb-000007
其中R为亲水基团,n1为0或正整数,n2为正整数,n3为0或正整数,n4为正整数,并且(n1+n2+n3)*n4=3~10。所述亲水基团选自羧基、羧盐、羟基、氨基、季铵盐、酯基、酰肼基、酰胺基、和磺酸基。
在一种具体的实施方式中,所述二醛为2-乙醇-己二醛。2-乙醇-己二醛通过以下方法合成:以3-环己烯-1-甲醇(CAS:1679-51-2)为原料,经过三步反应生成亲水性二醛2-乙醇-己二醛,反应过程如下:
Figure PCTCN2015091031-appb-000008
实施例4:
本实施例提供了一种QLED,其包括实施例2所述的图案化的方法制备的量子点层。
在一些实施方式中,QLED还包括阴极、阳极,以及阴极与阳极之间的电子注入层、电子传输层、空穴阻挡层、空穴传输层和空穴注入层;实施例2所述的图案化的方法制备的量子点作为发光层设于空穴阻挡层与空穴传输层之间。
实施例5:
本实施例提供一种量子点彩膜,所述量子点彩膜包括实施例2的图案化的方法制备的量子点层。
实施例6:
本实施例提供一种显示装置,所述显示装置包括实施例4的QLED或实施例5的量子点彩膜。
显然,上述各实施例的具体实施方式还可进行许多变化;例如:可以采用其它相类似的原料制备出含有亲水基团的亲水性二醛用于改性光刻胶,或者QLED的有机层可以根据实际需要进行改变等。
以上所述仅是本发明的示范性实施方式,而非用于限制本发明的保护范围,本发明的保护范围由所附的权利要求确定。
本申请要求于2015年6月16日递交的中国专利申请第201510335044.4号的优先权,在此全文引用上述中国专利申请公开的内容以作为本申请的一部分。

Claims (19)

  1. 一种量子点层图案化的方法,包括以下步骤:
    形成亲水光刻胶图案,包括:
    用光刻胶在基板上形成光刻胶材料层,
    对光刻胶材料层进行构图从而形成光刻胶图案,和
    对光刻胶进行亲水处理;
    涂布量子点;
    除去保留在光刻胶图案上的量子点;和
    剥离光刻胶图案。
  2. 根据权利要求1所述的量子点层图案化的方法,其中,
    所述对光刻胶进行亲水处理在形成光刻胶材料层之前进行;
    所述的形成亲水光刻胶图案包括:
    将光刻胶与亲水性二醛混合得到含有亲水基团的亲水性光刻胶;
    在基板上形成所述亲水性光刻胶材料层;和
    然后对所述亲水性光刻胶材料层进行构图从而形成光刻胶图案。
  3. 根据权利要求2所述的量子点层图案化的方法,其中,所述亲水性光刻胶中亲水性二醛含量为1-20wt%。
  4. 根据权利要求1所述的量子点层图案化的方法,其中,
    所述对光刻胶进行亲水处理在形成光刻胶材料层之后进行;
    对光刻胶进行亲水处理包括:
    配制含酸的亲水性二醛水溶液,所述亲水性二醛中含有亲水基团;
    将形成光刻胶材料层的基板浸泡于所述水溶液中;
    将基板加热,光刻胶材料层的表面形成亲水基团。
  5. 根据权利要求4所述的量子点层图案化的方法,其中,所述酸选自草酸、马来酸、马来酸酐、乙酸、三氯乙酸、苯磺酸、酒石酸、柠檬酸、和消旋苹果酸。
  6. 根据权利要求4或5所述的量子点层图案化的方法,其中,所述亲水性二醛水溶液的质量浓度为3~20wt%、pH为2~5.5。
  7. 根据权利要求4-6中任一项所述的量子点层图案化的方法,其中,所述浸泡的时间为5~30min。
  8. 根据权利要求4所述的量子点层图案化的方法,其中,所述将基板加热包括:在90~160℃的温度下加热5~60min。
  9. 根据权利要求2或4所述的量子点层图案化的方法,其中,所述亲水性二醛结构式为:
    Figure PCTCN2015091031-appb-100001
    其中R为亲水基团,n1为0或正整数,n2为正整数,n3为0或正整数,n4为正整数,并且(n1+n2+n3)*n4=3~10。
  10. 根据权利要求2-9中任一项所述的量子点层图案化的方法,其中,所述亲水基团选自羧基、羧盐、羟基、氨基、季铵盐、酯基、酰肼基、酰胺基、和磺酸基。
  11. 根据权利要求1-10中任一项所述的量子点层图案化的方法,其中,所述光刻胶包括酚醛树脂。
  12. 根据权利要求1所述的量子点层图案化的方法,其中所述方法还包括,在形成所述光刻胶材料层之前,对所述基板进行量子点锚定力处理。
  13. 根据权利要求1所述的量子点层图案化的方法,其中,所述光刻胶图案在基板上恰好暴露出需要涂覆量子点的区域。
  14. 一种量子点层图案化用光刻胶,其中,所述光刻胶含有亲水基团,其中所述亲水基团源自亲水性二醛。
  15. 根据权利要求14的量子点层图案化用光刻胶,其中,所述亲水性二醛的结构式为:
    Figure PCTCN2015091031-appb-100002
    其中R为亲水基团,n1为0或正整数,n2为正整数,n3为0或正整数,n4为正整数,并且(n1+n2+n3)*n4=3~10。
  16. 根据权利要求14或15的量子点层图案化用光刻胶,其中,所述亲水基团选自羧基、羧盐、羟基、氨基、季铵盐、酯基、酰肼基、酰胺基、和磺酸基。
  17. 一种量子点发光二极管(QLED),包括发光层,其中,所述发光层包括权利要求1-13任一项所述的量子点层图案化的方法制备的量子点层。
  18. 一种量子点彩膜,包括权利要求1-13任一项所述的量子点层图案化的方法制备的量子点层。
  19. 一种显示装置,包括权利要求17中所述的QLED或权利要求18中所述的量子点彩膜。
PCT/CN2015/091031 2015-06-16 2015-09-29 亲水光刻胶、量子点层图案化的方法及量子点发光二极管 WO2016201823A1 (zh)

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