WO2018049948A1 - Method for linking in quantum dot film and quantum dot film - Google Patents

Method for linking in quantum dot film and quantum dot film Download PDF

Info

Publication number
WO2018049948A1
WO2018049948A1 PCT/CN2017/096253 CN2017096253W WO2018049948A1 WO 2018049948 A1 WO2018049948 A1 WO 2018049948A1 CN 2017096253 W CN2017096253 W CN 2017096253W WO 2018049948 A1 WO2018049948 A1 WO 2018049948A1
Authority
WO
WIPO (PCT)
Prior art keywords
quantum dot
dot film
chain
film
quantum
Prior art date
Application number
PCT/CN2017/096253
Other languages
French (fr)
Chinese (zh)
Inventor
向超宇
曾世荣
Original Assignee
Tcl集团股份有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Tcl集团股份有限公司 filed Critical Tcl集团股份有限公司
Publication of WO2018049948A1 publication Critical patent/WO2018049948A1/en

Links

Images

Classifications

    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/10—Deposition of organic active material
    • H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/10—Deposition of organic active material
    • H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
    • H10K71/13—Deposition of organic active material using liquid deposition, e.g. spin coating using printing techniques, e.g. ink-jet printing or screen printing

Definitions

  • the invention relates to the field of quantum dots, in particular to a method for a plastic chain quantum dot film and a quantum dot film.
  • Colloid quantum dots are nanomaterial systems based on liquid phase distribution. Colloidal quantum dots are prepared by different preparation processes (spin coating, printing, transfer, coating, etc.) to prepare quantum dot multilayer or single layer films. In the colloidal quantum dot system, the quantum dots are dispersed in a solvent, and the solvent evaporates after film formation, forming a solid film in which only quantum dots are deposited. Quantum dots are linked by weak Van der Waals forces. Under external action (mechanical force, solvent, etc.), the film morphology cannot be maintained. Therefore, the application of colloidal quantum dots is greatly limited.
  • the quantum dots cannot be glued, they may be washed away by the solvent used in the preparation process above the quantum dot layer, thereby limiting the preparation process and material selection of the QLED, thereby restricting the properties and applications of the QLED. .
  • the solution of the quantum dot glue chain mainly uses a chemical method, that is, adding a chemical rubber chain group in the preparation process of the quantum dot, and forming a film, and then reacting the rubber chain group by heat treatment or light treatment, thereby forming a quantum dot film of the rubber chain.
  • the problem with this method is that the gum chain groups are typically chemically active groups whose presence can affect the properties of the quantum dots, such as luminescence efficiency, electron mobility, and the like.
  • by-products are produced during the chain process, and these by-products are difficult to remove as quantum impurities from the quantum dot film.
  • the object of the present invention is to provide a method for a plastic chain quantum dot film and a quantum dot film, which aims to solve the problem that the quantum dot chain method of the prior art affects quantum dot performance and many by-products. .
  • a method for a plastic chain quantum dot film comprising the steps of:
  • the colloidal quantum dots are prepared into one or more layers of quantum dot films, and after the film formation, the solvent in the quantum dot film is volatilized to form a quantum dot film with only quantum dots;
  • H 2 is introduced into the vacuum plasma generating chamber, and the introduced H 2 is converted into H plasma, and passed through a H plasma chain quantum dot film.
  • the colloidal quantum dots are prepared into one or more quantum dot films by spin coating, printing, transfer or coating.
  • the solvent is naturally volatilized or volatilized by heating.
  • the quantum dot film has a rubber chain time of 1 to 500 s.
  • step C by regulating H or the like
  • the intensity of the ions controls the rate of the gel of the quantum dot film.
  • Plastic chain quantum dot thin film method wherein, in step C, by the plasma strength H H 2 pressure regulated, when the plastic chain is controlled H 2 pressure 0.5 ⁇ 300mtorr.
  • the method of the invention adopts the HHIC glue chain quantum dot film, which has short time consumption, low requirement condition, no special requirement for the reactants, and no new substance is produced.
  • the film of the HHIC plastic chain of the present invention is superior in stability to the film of the conventional heated rubber chain, and its electrical properties are not changed, and the application of the solution method and the range of material selection can be expanded.
  • Figure 1 is a flow chart showing a preferred embodiment of a method for a plastic chain quantum dot film of the present invention.
  • Figure 2 is a schematic diagram showing the relationship between relative thickness and reaction time.
  • Figure 3 is a graphical representation of the relationship between the rate of the gum chain and the strength of the H plasma.
  • Fig. 4 is a comparison of fluorescence spectra of the ungelatinized quantum dot film before wiping and after immersion of the unbonded quantum dot film.
  • Fig. 5 is a comparison of fluorescence spectra of a plastic chain quantum dot film before wiping and after being wiped with a plastic dot film.
  • the present invention provides a method for a plastic chain quantum dot film and a quantum dot film.
  • FIG. 1 is a flow chart of a preferred embodiment of a method for a plastic chain quantum dot film of the present invention, as shown in the figure, comprising the steps of:
  • the colloidal quantum dots are prepared into one or more quantum dot films by spin coating, printing, transfer or coating.
  • Colloidal quantum dots are prepared by dispersing quantum dots in a solvent. After the film formation, the solvent naturally volatilizes or volatilizes by heating to form a quantum dot film with only quantum dots.
  • the HHIC technique uses H 2 as a starting reactant and converts the introduced H 2 into H plasma, and then opens a chemical bond such as CC, CH, CO, etc. with a suitable energy H plasma. These open chemical bonds are then rejoined to bond the chemicals together.
  • the method for the HHIC gel chain quantum dot film of the invention has a short time (several seconds) and a low requirement condition (room temperature), and there is no special requirement for the reactant. And no new substances will be produced.
  • the quantum dot film of the HHIC rubber chain of the present invention is superior in stability to the conventional quantum dot film of the heated rubber chain, and its electrical properties are not changed, and the application of the solution method and the selection range can be expanded.
  • the present invention also improves the glue chain process of the quantum dot film.
  • the thickness of the quantum dot film glue chain of the present invention is related to the chain time and the intensity of the H plasma.
  • the quantum dot film of the present invention preferably has a gel chain time of from 1 to 500 s.
  • Figure 2 shows the relative thickness (i.e. relative rubber chain thickness) obtained by simulation under certain conditions and the chain time.
  • the rubber chain reaction begins to concentrate on the surface of the quantum dot film, and there are many active radicals on the surface of the quantum dot film, so the relative thickness increases with the increase of the glue chain time.
  • the quantum dot film is basically glued and the relative thickness does not change.
  • the quantum dot film has a gel chain time of 10 to 20 s.
  • the quantum dot film has a rubber chain time of 15 s or 18 s.
  • the chain rate is related to the intensity of the H plasma, and the intensity of the H plasma is regulated by the gas pressure of hydrogen.
  • the gas pressure for controlling H 2 is from 0.5 to 300 mtorr. More preferably, the pressure of the hydrogen gas in the chain of the present invention is controlled to be 0.5 to 1.4 mtorr (e.g., 1 mtorr or 1.24 mtorr). This is because when the gas pressure of hydrogen is less than a specific intensity, the gas pressure of hydrogen shown in Fig.
  • the pressure of the hydrogen gas in the chain of the present invention is controlled to be 0.5 to 1.4 mtorr.
  • Figure 4 is a view of the ungelatinized quantum dot film before wiping and after unglue chain quantum dot film wiping Fluorescence spectrum comparison chart
  • Figure 5 is a comparison of fluorescence spectra of the glue chain quantum dot film before wiping and the glue chain quantum dot film wiping.
  • the quantum dot film is wiped with a cotton swab dipped with a quantum dot solvent.
  • the cotton swab wipes the mechanical force and solvent.
  • the ungelled-chain quantum dot film was completely removed after wiping without a fluorescent signal.
  • the plastic chain quantum dot film still has a fluorescent signal after wiping, because the plastic chain quantum dot film effectively resists mechanical force and solvent.
  • the present invention also provides a quantum dot film which is formed by a method of a rubber chain quantum dot film as described above.
  • the quantum dot film of the HHIC glue chain has better solvent resistance and mechanical loss resistance.
  • the quantum dot film of the HHIC rubber chain is superior to the traditional quantum dot film of the heated rubber chain in stability.
  • a 10 mg/ml quantum dot solution QD1 was dispensed and spin coated onto a glass substrate in a nitrogen atmosphere.
  • the spin coating conditions were 6000 rpm, 60 s, forming a quantum dot film of about 10 nm.
  • the quantum dot film is transported into the HHIC vacuum plasma generating chamber, pumped to a working pressure of 1.5*10 -3 Torr, and fed with 20 SCCM of hydrogen, the electron acceleration voltage is -100 V, and the hysteresis voltage is +100 V to -50 V. After the reaction for 40 s, the sample was taken out. After the sample chain is broken, it cannot be wiped off with the same solvent.
  • a 30 mg/ml quantum dot solution QD2 was placed, and the same solvent was used in solution QD1.
  • the spin coating conditions were 3000 rpm for 60 s to form a quantum dot film.
  • the quantum dot film is transported into the HHIC vacuum plasma generating chamber, pumped to a working pressure of 1.5*10 -2 Torr, and fed with 20 SCCM of hydrogen, the electron accelerating voltage is -100 V, and the hysteresis voltage is +100 V to -50 V.
  • the sample was taken after 160 s of reaction. The total thickness of the sample was 50 nm. Cannot be washed by the same solvent.
  • the quantum dot solution was prepared: a quantum dot solution QD1 of 40 mg/ml and a quantum dot solution QD2 of 60 mg/ml. Spin on a glass substrate in a nitrogen atmosphere. The spin coating conditions were 2000 rpm, 60 s, to form a 120 nm quantum dot film. The quantum dot film is transported into the HHIC vacuum plasma generating chamber, pumped to a working pressure of 1.5*10 -1 Torr, and passed through 55 SCCM of hydrogen, the electron accelerating voltage is -100 V, and the hysteresis voltage is +100 V to -50 V. After the reaction for 400 s, the sample was taken out. After the sample chain, it cannot be cleaned by the same solvent.
  • the present invention provides a method for a plastic chain quantum dot film and a quantum dot film.
  • the invention adopts a HHIC plastic chain quantum dot film, and improves the process thereof, so that the quantum dot film has better solvent resistance and The role of mechanical force.
  • the method of the HHIC gel chain quantum dot film of the invention has short time and low requirement, and has no special requirements on the reactants. And no new substances will be produced.
  • the film of the HHIC gel chain of the present invention is superior in stability to the film of the conventional heated rubber chain, and its electrical properties are not changed. HHIC can expand the application of the solution method and the range of materials selected.

Abstract

A method for linking in a quantum dot film and a quantum dot film. The method comprises the steps of: preparing colloidal quantum dots into one or more layers of quantum dot films, and volatilizing a solvent in the quantum dot film after film-forming, to form a quantum dot film containing only quantum dots (S100); placing the quantum dot film in a vacuum plasma generating chamber (S200); and introducing H2 into the vacuum plasma generating chamber, converting H2 to H plasma, and performing linking in the quantum dot film by using the H plasma (S300). HHIC is adopted for linking in the quantum dot film, and a process thereof is improved, so that the quantum dot film has better performance in terms of solvent resistance and mechanical force resistance. The method for linking in a quantum dot film by HHIC requires a short time, and has low requirements for conditions and no special requirements for reactants, and will not produce new substances. In addition, a film that has undergone linking by HHIC is superior in stability compared to conventional heat-linked films, and electrical properties thereof are unchanged. HHIC can expand the application and material selection scopes of solution methods.

Description

一种胶链量子点薄膜的方法与量子点薄膜Method for plastic chain quantum dot film and quantum dot film 技术领域Technical field
本发明涉及量子点领域，尤其涉及一种胶链量子点薄膜的方法与量子点薄膜。The invention relates to the field of quantum dots, in particular to a method for a plastic chain quantum dot film and a quantum dot film.
背景技术Background technique
胶体(Colloid)量子点是基于液相分布的纳米材料体系。胶体量子点通过不同的制备工艺(旋涂，打印，转印，涂布等)，制备量子点多层或单层薄膜。由于胶体量子点体系中，量子点分散在溶剂中，成膜后溶剂挥发，形成只有量子点堆积的固体薄膜。量子点之间以微弱的范德华力链接，在外界作用下(机械力，溶剂等)，薄膜形态不能保持。因此胶体量子点的应用受到很大限制。例如在QLED的制备过程中，由于量子点无法胶链，可能被量子点层之上的制备过程用的溶剂冲走，因此限制了QLED的制备工艺和材料选择，从而制约了QLED的性质和应用。Colloid quantum dots are nanomaterial systems based on liquid phase distribution. Colloidal quantum dots are prepared by different preparation processes (spin coating, printing, transfer, coating, etc.) to prepare quantum dot multilayer or single layer films. In the colloidal quantum dot system, the quantum dots are dispersed in a solvent, and the solvent evaporates after film formation, forming a solid film in which only quantum dots are deposited. Quantum dots are linked by weak Van der Waals forces. Under external action (mechanical force, solvent, etc.), the film morphology cannot be maintained. Therefore, the application of colloidal quantum dots is greatly limited. For example, in the preparation process of QLED, since the quantum dots cannot be glued, they may be washed away by the solvent used in the preparation process above the quantum dot layer, thereby limiting the preparation process and material selection of the QLED, thereby restricting the properties and applications of the QLED. .
目前量子点胶链的解决方案主要运用化学方法，即在量子点制备过程中添加化学胶链基团，成膜后通过热处理或者光处理，使胶链基团反应，从而胶链量子点薄膜。此方法的问题是胶链基团通常是化学活性很强的基团，它们的存在能够影响量子点的性质，如发光效率，电子迁移率等。其次在胶链过程中产生副产物，这些副产物作为杂质很难从量子点薄膜中去除。 At present, the solution of the quantum dot glue chain mainly uses a chemical method, that is, adding a chemical rubber chain group in the preparation process of the quantum dot, and forming a film, and then reacting the rubber chain group by heat treatment or light treatment, thereby forming a quantum dot film of the rubber chain. The problem with this method is that the gum chain groups are typically chemically active groups whose presence can affect the properties of the quantum dots, such as luminescence efficiency, electron mobility, and the like. Secondly, by-products are produced during the chain process, and these by-products are difficult to remove as quantum impurities from the quantum dot film.
因此，现有技术还有待于改进和发展。Therefore, the prior art has yet to be improved and developed.
发明内容Summary of the invention
鉴于上述现有技术的不足，本发明的目的在于提供一种胶链量子点薄膜的方法与量子点薄膜，旨在解决现有技术的量子点胶链方法影响量子点性能、副产物多的问题。In view of the above deficiencies of the prior art, the object of the present invention is to provide a method for a plastic chain quantum dot film and a quantum dot film, which aims to solve the problem that the quantum dot chain method of the prior art affects quantum dot performance and many by-products. .
本发明的技术方案如下：The technical solution of the present invention is as follows:
一种胶链量子点薄膜的方法，其中，包括步骤：A method for a plastic chain quantum dot film, comprising the steps of:
A、将胶体量子点制备成一层或多层量子点薄膜，成膜后将量子点薄膜中的溶剂挥发，形成只有量子点的量子点薄膜；A. The colloidal quantum dots are prepared into one or more layers of quantum dot films, and after the film formation, the solvent in the quantum dot film is volatilized to form a quantum dot film with only quantum dots;
B、将量子点薄膜放入真空等离子体发生腔体；B. placing the quantum dot film into a vacuum plasma generating chamber;
C、在真空等离子体发生腔体内通入H2，并使通入的H2转变成H等离子，通过H等离子胶链量子点薄膜。C. H 2 is introduced into the vacuum plasma generating chamber, and the introduced H 2 is converted into H plasma, and passed through a H plasma chain quantum dot film.
所述的胶链量子点薄膜的方法，其中，步骤A中，通过旋涂、打印、转印或涂布的方式，将胶体量子点制备成一层或多层量子点薄膜。In the method of the plastic chain quantum dot film, in the step A, the colloidal quantum dots are prepared into one or more quantum dot films by spin coating, printing, transfer or coating.
所述的胶链量子点薄膜的方法，其中，步骤A中，溶剂自然挥发或通过加热方式挥发。In the method of the plastic chain quantum dot film, in the step A, the solvent is naturally volatilized or volatilized by heating.
所述的胶链量子点薄膜的方法，其中，步骤C中，量子点薄膜的胶链时间为1～500s。In the method of the plastic chain quantum dot film, in the step C, the quantum dot film has a rubber chain time of 1 to 500 s.
所述的胶链量子点薄膜的方法，其中，量子点薄膜的胶链时间为10～20s。The method for the plastic chain quantum dot film, wherein the quantum dot film has a rubber chain time of 10 to 20 s.
所述的胶链量子点薄膜的方法，其中，步骤C中，通过调控H等 离子的强度控制量子点薄膜的胶链速率。The method for the rubber chain quantum dot film, wherein, in step C, by regulating H or the like The intensity of the ions controls the rate of the gel of the quantum dot film.
所述的胶链量子点薄膜的方法，其中，步骤C中，H等离子的强度由H2的气压调控，胶链时控制H2的气压为0.5～300mtorr。Plastic chain quantum dot thin film method, wherein, in step C, by the plasma strength H H 2 pressure regulated, when the plastic chain is controlled H 2 pressure 0.5 ~ 300mtorr.
所述的胶链量子点薄膜的方法，其中，胶链时控制H2的气压为1～1.4mtorr。The method for the plastic chain quantum dot film, wherein the pressure of the H 2 is controlled to be 1 to 1.4 mtorr at the time of the rubber chain.
一种量子点薄膜，其中，采用如上任一所述的胶链量子点薄膜的方法胶链而成。A quantum dot film formed by a method of using a rubber chain quantum dot film as described above.
有益效果：本发明采用HHIC胶链量子点薄膜的方法，其耗时短，条件要求低，对反应物没有特殊要求，而且不会产生新的物质。另外，本发明经过HHIC胶链的薄膜在稳定性上优于传统加热胶链的薄膜，并且其电学性质没有变化，能够扩大溶液法的应用和选材范围。Advantageous Effects: The method of the invention adopts the HHIC glue chain quantum dot film, which has short time consumption, low requirement condition, no special requirement for the reactants, and no new substance is produced. In addition, the film of the HHIC plastic chain of the present invention is superior in stability to the film of the conventional heated rubber chain, and its electrical properties are not changed, and the application of the solution method and the range of material selection can be expanded.
附图说明DRAWINGS
图1为本发明的一种胶链量子点薄膜的方法较佳实施例的流程图。BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a flow chart showing a preferred embodiment of a method for a plastic chain quantum dot film of the present invention.
图2为相对厚度和反应时间的关系示意图。Figure 2 is a schematic diagram showing the relationship between relative thickness and reaction time.
图3为胶链速率和H等离子的强度的关系示意图。Figure 3 is a graphical representation of the relationship between the rate of the gum chain and the strength of the H plasma.
图4是未胶链量子点薄膜擦拭前和未胶链量子点薄膜擦拭后的荧光光谱对比图。Fig. 4 is a comparison of fluorescence spectra of the ungelatinized quantum dot film before wiping and after immersion of the unbonded quantum dot film.
图5为胶链量子点薄膜擦拭前和胶链量子点薄膜擦拭后的荧光光谱对比图。Fig. 5 is a comparison of fluorescence spectra of a plastic chain quantum dot film before wiping and after being wiped with a plastic dot film.
具体实施方式 detailed description
本发明提供一种胶链量子点薄膜的方法与量子点薄膜，为使本发明的目的、技术方案及效果更加清楚、明确，以下对本发明进一步详细说明。应当理解，此处所描述的具体实施例仅仅用以解释本发明，并不用于限定本发明。The present invention provides a method for a plastic chain quantum dot film and a quantum dot film. In order to make the objects, technical solutions and effects of the present invention more clear and clear, the present invention will be further described in detail below. It is understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
图1为本发明的一种胶链量子点薄膜的方法较佳实施例的流程图，如图所示，其包括步骤：1 is a flow chart of a preferred embodiment of a method for a plastic chain quantum dot film of the present invention, as shown in the figure, comprising the steps of:
S100、将胶体量子点制备成一层或多层量子点薄膜，成膜后将量子点薄膜中的溶剂挥发，形成只有量子点的量子点薄膜；S100, preparing colloidal quantum dots into one or more layers of quantum dot films, and volatilizing a solvent in the quantum dot film after forming a film to form a quantum dot film having only quantum dots;
步骤S100中，通过旋涂、打印、转印或涂布等方式，将胶体量子点制备成一层或多层量子点薄膜。胶体量子点是量子点分散在溶剂中配制而成的，成膜后溶剂自然挥发或通过加热的方式挥发，形成只有量子点堆积的量子点薄膜。In step S100, the colloidal quantum dots are prepared into one or more quantum dot films by spin coating, printing, transfer or coating. Colloidal quantum dots are prepared by dispersing quantum dots in a solvent. After the film formation, the solvent naturally volatilizes or volatilizes by heating to form a quantum dot film with only quantum dots.
S200、将量子点薄膜放入真空等离子体发生腔体；S200, placing a quantum dot film into a vacuum plasma generating cavity;
S300、在真空等离子体发生腔体内通入H2，并使通入的H2转变成H等离子，通过H等离子胶链量子点薄膜。S300, introducing H 2 into the vacuum plasma generating chamber, and converting the introduced H 2 into H plasma, and passing through the H plasma chain quantum dot film.
HHIC技术是通过H2作为起始反应剂，并使通入的H2转变成H等离子，然后以适合能量的H等离子打开C-C，C-H，C-O等化学键。之后这些打开的化学键重新接合，从而把化学物质胶链在一起。本发明HHIC胶链量子点薄膜的方法，其耗时短(几秒钟)，条件要求低(室温)，对反应物没有特殊要求。而且不会产生新的物质。另外，本发明经过HHIC胶链的量子点薄膜在稳定性上优于传统加热胶链的量子点薄膜，并且其电学性质没有变化，能够扩大溶液法的应用和选材范 围。The HHIC technique uses H 2 as a starting reactant and converts the introduced H 2 into H plasma, and then opens a chemical bond such as CC, CH, CO, etc. with a suitable energy H plasma. These open chemical bonds are then rejoined to bond the chemicals together. The method for the HHIC gel chain quantum dot film of the invention has a short time (several seconds) and a low requirement condition (room temperature), and there is no special requirement for the reactant. And no new substances will be produced. In addition, the quantum dot film of the HHIC rubber chain of the present invention is superior in stability to the conventional quantum dot film of the heated rubber chain, and its electrical properties are not changed, and the application of the solution method and the selection range can be expanded.
除了采用HHIC胶链量子点薄膜方法外，本发明还对量子点薄膜的胶链工艺进行了改进。本发明量子点薄膜胶链的厚度与胶链时间和H等离子的强度有关。本发明量子点薄膜的胶链时间优选为1～500s。图2显示了在一定条件下，通过模拟得到的相对厚度(即相对胶链厚度)和胶链时间的关系。胶链反应开始集中于量子点薄膜的表面，量子点薄膜表面的活性自由基会很多，因此相对厚度随着胶链时间的增加而增加。反应一段时间后，量子点薄膜基本被胶链，相对厚度不在变化。更优选地，量子点薄膜的胶链时间为10～20s，例如，量子点薄膜的胶链时间为15s或18s。In addition to the HHIC glue chain quantum dot film method, the present invention also improves the glue chain process of the quantum dot film. The thickness of the quantum dot film glue chain of the present invention is related to the chain time and the intensity of the H plasma. The quantum dot film of the present invention preferably has a gel chain time of from 1 to 500 s. Figure 2 shows the relative thickness (i.e. relative rubber chain thickness) obtained by simulation under certain conditions and the chain time. The rubber chain reaction begins to concentrate on the surface of the quantum dot film, and there are many active radicals on the surface of the quantum dot film, so the relative thickness increases with the increase of the glue chain time. After a period of reaction, the quantum dot film is basically glued and the relative thickness does not change. More preferably, the quantum dot film has a gel chain time of 10 to 20 s. For example, the quantum dot film has a rubber chain time of 15 s or 18 s.
本发明胶链量子点薄膜时，胶链速率与H等离子的强度有关，而该H等离子的强度由氢气的气压调控。随着H等离子的强度降低，胶链速率减慢；随着H等离子的强度增高，胶链速率加快。优选地，本发明胶链时，控制H2的气压为0.5～300mtorr。更优选地，本发明胶链时控制氢气的气压为0.5～1.4mtorr(如1mtorr或1.24mtorr)。这是因为在氢气的气压小于特定强度下，如图3所示的氢气的气压小于0.5mtorr下，H等离子的强度太低，胶链速率很慢。氢气的气压超过特定强度，如图3所示的氢气的气压大于0.5mtorr下，H等离子的强度太高，胶链速率迅速增加。不考虑薄膜有限厚度的情况下，胶链速率持续增大。实际情况中，过大的氢气气压下，等离子电流增大，造成不稳定。因此，本发明胶链时控制氢气的气压为0.5～1.4mtorr。In the gel chain quantum dot film of the present invention, the chain rate is related to the intensity of the H plasma, and the intensity of the H plasma is regulated by the gas pressure of hydrogen. As the intensity of the H plasma decreases, the rate of the gel chain decreases; as the intensity of the H plasma increases, the rate of the gel chain increases. Preferably, in the chain of the present invention, the gas pressure for controlling H 2 is from 0.5 to 300 mtorr. More preferably, the pressure of the hydrogen gas in the chain of the present invention is controlled to be 0.5 to 1.4 mtorr (e.g., 1 mtorr or 1.24 mtorr). This is because when the gas pressure of hydrogen is less than a specific intensity, the gas pressure of hydrogen shown in Fig. 3 is less than 0.5 mtorr, the intensity of H plasma is too low, and the rate of the rubber chain is very slow. The gas pressure of hydrogen exceeds a certain intensity. When the gas pressure of hydrogen shown in FIG. 3 is greater than 0.5 mtorr, the intensity of H plasma is too high, and the rate of the rubber chain increases rapidly. The rate of the gum chain continues to increase regardless of the limited thickness of the film. In actual conditions, under too much hydrogen pressure, the plasma current increases, causing instability. Therefore, the pressure of the hydrogen gas in the chain of the present invention is controlled to be 0.5 to 1.4 mtorr.
图4是未胶链量子点薄膜擦拭前和未胶链量子点薄膜擦拭后的 荧光光谱对比图，图5为胶链量子点薄膜擦拭前和胶链量子点薄膜擦拭后的荧光光谱对比图。量子点成膜后，应用沾有量子点溶剂的棉签擦拭量子点薄膜。棉签擦拭有机械力和溶剂的作用。如图4所示，未胶链量子点薄膜在擦拭后完全移除，没有荧光信号。如图5所示，胶链量子点薄膜在擦拭后，仍有荧光信号，这是因为胶链量子点薄膜有效抵挡机械力和溶剂的作用。Figure 4 is a view of the ungelatinized quantum dot film before wiping and after unglue chain quantum dot film wiping Fluorescence spectrum comparison chart, Figure 5 is a comparison of fluorescence spectra of the glue chain quantum dot film before wiping and the glue chain quantum dot film wiping. After the quantum dots are formed into a film, the quantum dot film is wiped with a cotton swab dipped with a quantum dot solvent. The cotton swab wipes the mechanical force and solvent. As shown in Figure 4, the ungelled-chain quantum dot film was completely removed after wiping without a fluorescent signal. As shown in Fig. 5, the plastic chain quantum dot film still has a fluorescent signal after wiping, because the plastic chain quantum dot film effectively resists mechanical force and solvent.
本发明还提供一种量子点薄膜，其采用如上任一所述的胶链量子点薄膜的方法胶链而成。通过HHIC胶链的量子点薄膜，具有更好的抗溶剂和抗机械损耗性能。且经过HHIC胶链的量子点薄膜在稳定性上优于传统加热胶链的量子点薄膜。The present invention also provides a quantum dot film which is formed by a method of a rubber chain quantum dot film as described above. The quantum dot film of the HHIC glue chain has better solvent resistance and mechanical loss resistance. The quantum dot film of the HHIC rubber chain is superior to the traditional quantum dot film of the heated rubber chain in stability.
下面通过实施例对本发明进行详细说明。The invention will now be described in detail by way of examples.
实施例1Example 1
配置10mg/ml的量子点溶液QD1，在氮气环境中旋涂于玻璃基底上。旋涂条件为6000rpm，60s，形成约10nm的量子点薄膜。将量子点薄膜传输到HHIC真空等离子体发生腔体内，抽到1.5*10-3Torr的工作气压，通入20SCCM的氢气，电子加速电压为-100V，迟滞电压为+100V到-50V的条件下，反应40s后取出样品。样品胶链后，无法用相同溶剂擦拭掉。A 10 mg/ml quantum dot solution QD1 was dispensed and spin coated onto a glass substrate in a nitrogen atmosphere. The spin coating conditions were 6000 rpm, 60 s, forming a quantum dot film of about 10 nm. The quantum dot film is transported into the HHIC vacuum plasma generating chamber, pumped to a working pressure of 1.5*10 -3 Torr, and fed with 20 SCCM of hydrogen, the electron acceleration voltage is -100 V, and the hysteresis voltage is +100 V to -50 V. After the reaction for 40 s, the sample was taken out. After the sample chain is broken, it cannot be wiped off with the same solvent.
实施例2Example 2
配置30mg/ml的量子点溶液QD2，于溶液QD1用相同的溶剂。在氮气环境中旋涂于上述QD1的样品上。旋涂条件为3000rpm，60s，形成量子点薄膜。将量子点薄膜传输到HHIC真空等离子体发生腔体 内，抽到1.5*10-2Torr的工作气压，通入20SCCM的氢气，电子加速电压为-100V，迟滞电压为+100V到-50V的条件下，反应160s后取出样品。样品总厚度50nm。无法被相同溶剂清洗。A 30 mg/ml quantum dot solution QD2 was placed, and the same solvent was used in solution QD1. Spin-coated on the sample of QD1 above in a nitrogen atmosphere. The spin coating conditions were 3000 rpm for 60 s to form a quantum dot film. The quantum dot film is transported into the HHIC vacuum plasma generating chamber, pumped to a working pressure of 1.5*10 -2 Torr, and fed with 20 SCCM of hydrogen, the electron accelerating voltage is -100 V, and the hysteresis voltage is +100 V to -50 V. The sample was taken after 160 s of reaction. The total thickness of the sample was 50 nm. Cannot be washed by the same solvent.
实施例3Example 3
配置量子点溶液：40mg/ml的量子点溶液QD1和60mg/ml的量子点溶液QD2。在氮气环境中旋涂于玻璃基底上。旋涂条件为2000rpm，60s，形成120nm的量子点薄膜。将量子点薄膜传输到HHIC真空等离子体发生腔体内，抽到1.5*10-1Torr的工作气压，通入55SCCM的氢气，电子加速电压为-100V，迟滞电压为+100V到-50V的条件下，反应400s后取出样品。样品胶链后，无法被相同溶剂清洗。The quantum dot solution was prepared: a quantum dot solution QD1 of 40 mg/ml and a quantum dot solution QD2 of 60 mg/ml. Spin on a glass substrate in a nitrogen atmosphere. The spin coating conditions were 2000 rpm, 60 s, to form a 120 nm quantum dot film. The quantum dot film is transported into the HHIC vacuum plasma generating chamber, pumped to a working pressure of 1.5*10 -1 Torr, and passed through 55 SCCM of hydrogen, the electron accelerating voltage is -100 V, and the hysteresis voltage is +100 V to -50 V. After the reaction for 400 s, the sample was taken out. After the sample chain, it cannot be cleaned by the same solvent.
综上所述，本发明提供的一种胶链量子点薄膜的方法与量子点薄膜，本发明采用HHIC胶链量子点薄膜，并改进了其工艺，使量子点薄膜有更好的抗溶剂和机械力的作用。本发明HHIC胶链量子点薄膜的方法耗时短，条件要求低，对反应物没有特殊要求。而且不会产生新的物质。另外，本发明经过HHIC胶链的薄膜在稳定性上优于传统加热胶链的薄膜，并且其电学性质没有变化。HHIC能够扩大溶液法的应用和选材范围。In summary, the present invention provides a method for a plastic chain quantum dot film and a quantum dot film. The invention adopts a HHIC plastic chain quantum dot film, and improves the process thereof, so that the quantum dot film has better solvent resistance and The role of mechanical force. The method of the HHIC gel chain quantum dot film of the invention has short time and low requirement, and has no special requirements on the reactants. And no new substances will be produced. In addition, the film of the HHIC gel chain of the present invention is superior in stability to the film of the conventional heated rubber chain, and its electrical properties are not changed. HHIC can expand the application of the solution method and the range of materials selected.
应当理解的是，本发明的应用不限于上述的举例，对本领域普通技术人员来说，可以根据上述说明加以改进或变换，所有这些改进和变换都应属于本发明所附权利要求的保护范围。 It is to be understood that the application of the present invention is not limited to the above-described examples, and those skilled in the art can make modifications and changes in accordance with the above description, all of which are within the scope of the appended claims.

Claims (15)

  1. 一种胶链量子点薄膜的方法，其特征在于，包括步骤：A method for a plastic chain quantum dot film, comprising the steps of:
    A、将胶体量子点制备成一层或多层量子点薄膜，成膜后将量子点薄膜中的溶剂挥发，形成只有量子点的量子点薄膜；A. The colloidal quantum dots are prepared into one or more layers of quantum dot films, and after the film formation, the solvent in the quantum dot film is volatilized to form a quantum dot film with only quantum dots;
    B、将量子点薄膜放入真空等离子体发生腔体；B. placing the quantum dot film into a vacuum plasma generating chamber;
    C、在真空等离子体发生腔体内通入H2，并使通入的H2转变成H等离子，通过H等离子胶链量子点薄膜。C. H 2 is introduced into the vacuum plasma generating chamber, and the introduced H 2 is converted into H plasma, and passed through a H plasma chain quantum dot film.
  2. 根据权利要求1所述的胶链量子点薄膜的方法，其特征在于，步骤A中，通过旋涂、打印、转印或涂布的方式，将胶体量子点制备成一层或多层量子点薄膜。The method of claim 1 , wherein in step A, the colloidal quantum dots are prepared into one or more quantum dot films by spin coating, printing, transfer or coating. .
  3. 根据权利要求1所述的胶链量子点薄膜的方法，其特征在于，步骤A中，溶剂自然挥发或通过加热方式挥发。The method of claim 1, wherein in step A, the solvent is naturally volatilized or volatilized by heating.
  4. 根据权利要求1所述的胶链量子点薄膜的方法，其特征在于，步骤C中，量子点薄膜的胶链时间为1～500s。The method of claim 1, wherein in the step C, the quantum dot film has a gel chain time of from 1 to 500 s.
  5. 根据权利要求4所述的胶链量子点薄膜的方法，其特征在于，量子点薄膜的胶链时间为10～20s。The method of claim 4, wherein the quantum dot film has a gum chain time of 10 to 20 s.
  6. 根据权利要求1所述的胶链量子点薄膜的方法，其特征在于，步骤C中，通过调控H等离子的强度控制量子点薄膜的胶链速率。The method of claim 1, wherein in step C, the rate of the gel of the quantum dot film is controlled by adjusting the intensity of the H plasma.
  7. 根据权利要求6所述的胶链量子点薄膜的方法，其特征在于，步骤C中，H等离子的强度由H2的气压调控，胶链时控制H2的气压为0.5～300mtorr。The method of quantum dot chain plastic film according to claim 6, wherein, in step C, by the plasma strength H H 2 gas pressure regulation, the control H 2 pressure of 0.5 ~ 300mtorr when plastic chain.
  8. 根据权利要求7所述的胶链量子点薄膜的方法，其特征在于，胶链时控制H2的气压为1～1.4mtorr。 The method of claim 7, wherein the pressure of the H 2 is controlled to be from 1 to 1.4 mtorr.
  9. 根据权利要求4所述的胶链量子点薄膜的方法，其特征在于，步骤C中，通过调控H等离子的强度控制量子点薄膜的胶链速率。The method of claim 4, wherein in step C, the rate of the gel of the quantum dot film is controlled by adjusting the intensity of the H plasma.
  10. 根据权利要求9所述的胶链量子点薄膜的方法，其特征在于，步骤C中，H等离子的强度由H2的气压调控，胶链时控制H2的气压为0.5～300mtorr。The method of quantum dot chain plastic film according to claim 9, wherein, in step C, by the plasma strength H H 2 gas pressure regulation, the control H 2 pressure of 0.5 ~ 300mtorr when plastic chain.
  11. 根据权利要求10所述的胶链量子点薄膜的方法，其特征在于，胶链时控制H2的气压为1～1.4mtorr。The method of claim 10, wherein the pressure of the H 2 is controlled to be from 1 to 1.4 mtorr.
  12. 根据权利要求11所述的胶链量子点薄膜的方法，其特征在于，量子点薄膜的胶链时间为10～20s。The method of claim 11, wherein the quantum dot film has a gum chain time of 10 to 20 s.
  13. 根据权利要求2所述的胶链量子点薄膜的方法，其特征在于，步骤A中，通过打印的方式，将胶体量子点制备成一层或多层量子点薄膜。The method of claim 2, wherein in step A, the colloidal quantum dots are prepared as one or more quantum dot films by printing.
  14. 一种量子点薄膜，其特征在于，采用如权利要求1～13任一所述的胶链量子点薄膜的方法胶链而成。A quantum dot film obtained by a method of using a rubber chain quantum dot film according to any one of claims 1 to 13 in a rubber chain.
  15. 一种QLED器件，其特征在于，所述QLED器件包括如权利要求14所述的量子点薄膜。 A QLED device characterized in that the QLED device comprises the quantum dot film of claim 14.
PCT/CN2017/096253 2016-09-18 2017-08-07 Method for linking in quantum dot film and quantum dot film WO2018049948A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201610827641.3 2016-09-18
CN201610827641.3A CN106229426B (en) 2016-09-18 2016-09-18 A kind of method and quantum dot film of glue chain quantum dot film

Publications (1)

Publication Number Publication Date
WO2018049948A1 true WO2018049948A1 (en) 2018-03-22

Family

ID=58075594

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2017/096253 WO2018049948A1 (en) 2016-09-18 2017-08-07 Method for linking in quantum dot film and quantum dot film

Country Status (2)

Country Link
CN (1) CN106229426B (en)
WO (1) WO2018049948A1 (en)

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106229426B (en) * 2016-09-18 2019-06-04 Tcl集团股份有限公司 A kind of method and quantum dot film of glue chain quantum dot film
CN109148701A (en) * 2017-06-19 2019-01-04 Tcl集团股份有限公司 The mixed film and preparation method and QLED device of quantum dot and carrier crosslinking
CN109148703B (en) * 2017-06-19 2020-10-27 Tcl科技集团股份有限公司 Inorganic matter coated quantum dot mixed film and preparation method thereof, and QLED
CN109148731B (en) * 2017-06-19 2020-07-21 Tcl科技集团股份有限公司 Quantum dot and carbon nano material crosslinked film, preparation method and Q L ED
CN109148699B (en) * 2017-06-19 2020-03-31 Tcl集团股份有限公司 Quantum dot and polymer crosslinked mixed film, preparation method and QLED
CN109148735A (en) * 2017-06-19 2019-01-04 Tcl集团股份有限公司 A kind of preparation method and photoelectric device of multi-layer quantum point film
CN109148734B (en) * 2017-06-19 2020-09-22 Tcl科技集团股份有限公司 Quantum dot and metal nanoparticle crosslinked film and preparation method and application thereof
WO2018233355A1 (en) * 2017-06-19 2018-12-27 Tcl集团股份有限公司 Mixed film and preparation method therefor, and preparation method for oled device
CN109148700B (en) * 2017-06-19 2020-07-17 Tcl科技集团股份有限公司 Quantum dot and inorganic nanoparticle crosslinked film and preparation method and application thereof
CN109148702B (en) * 2017-06-19 2020-07-21 Tcl科技集团股份有限公司 Quantum dot and carrier cross-linked mixed film, preparation method thereof and Q L ED device
CN109148698B (en) * 2017-06-19 2020-05-05 Tcl科技集团股份有限公司 Quantum dot and carrier crosslinked mixed film, preparation method and QLED device
CN108054285B (en) * 2017-12-12 2020-06-05 深圳市华星光电技术有限公司 Preparation method of quantum dot film, electroluminescent device and preparation method thereof

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20070125983A1 (en) * 2001-07-20 2007-06-07 Invitrogen Corporation Methods for the preparation of luminescent nanoparticles using two solvents
CN101033300A (en) * 2006-11-07 2007-09-12 郑直 Chemical method for preparing crosslinking polymer thin film
US8969470B1 (en) * 2013-06-12 2015-03-03 The Mitre Corporation Quantum dot-polymer nanocomposite for optical sensing
CN105185918A (en) * 2015-08-27 2015-12-23 Tcl集团股份有限公司 Quantum dot light-emitting layer, preparation method thereof and QLED
CN105779968A (en) * 2016-03-16 2016-07-20 华中科技大学 Preparation method of quantum dot film
CN106229426A (en) * 2016-09-18 2016-12-14 Tcl集团股份有限公司 The method of one brood lac chain quantum dot film and quantum dot film

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20070125983A1 (en) * 2001-07-20 2007-06-07 Invitrogen Corporation Methods for the preparation of luminescent nanoparticles using two solvents
CN101033300A (en) * 2006-11-07 2007-09-12 郑直 Chemical method for preparing crosslinking polymer thin film
US8969470B1 (en) * 2013-06-12 2015-03-03 The Mitre Corporation Quantum dot-polymer nanocomposite for optical sensing
CN105185918A (en) * 2015-08-27 2015-12-23 Tcl集团股份有限公司 Quantum dot light-emitting layer, preparation method thereof and QLED
CN105779968A (en) * 2016-03-16 2016-07-20 华中科技大学 Preparation method of quantum dot film
CN106229426A (en) * 2016-09-18 2016-12-14 Tcl集团股份有限公司 The method of one brood lac chain quantum dot film and quantum dot film

Also Published As

Publication number Publication date
CN106229426A (en) 2016-12-14
CN106229426B (en) 2019-06-04

Similar Documents

Publication Publication Date Title
WO2018049948A1 (en) Method for linking in quantum dot film and quantum dot film
CN108559972B (en) Preparation method of large-area single-layer tungsten disulfide film based on atmospheric pressure chemical vapor deposition and product
US5491114A (en) Method of making large-area semiconductor thin films formed at low temperature using nanocrystal presursors
US20140308822A1 (en) Deposition technique for depositing a coating on a device
JP6263450B2 (en) Organic monomolecular film formation method
CN106044855B (en) One kind prepares individual layer MoS2Method
TWI748147B (en) Method for making graphene adhesive film and method for transferring graphene
CN109735886B (en) Wide-spectrum anti-reflection film based on anodic aluminum oxide template and preparation method thereof
KR101807459B1 (en) Self-healing method of self-healing polymer using defect-healed reduced graphene oxide heater
JP4214250B2 (en) Method and apparatus for producing silicon nanocrystal structure
JPH11172418A (en) Film forming device
CN108546929A (en) A kind of method, the substrate with film and its application preparing titanium nitride nano film in substrate surface
CN105154848A (en) Method for preparing nitrogen oxygen silicon thin film
KR101523849B1 (en) Method of fabricating metal-carbon composite particle
CN112844064A (en) Disilane precursor silicon dioxide composite membrane, preparation method and application thereof
CN105154857A (en) One-step method wrinkling membrane preparation technology
CN110607516A (en) Preparation method of single-layer or double-layer tungsten disulfide film
RU2661166C2 (en) Method for creating transparent conductive composite nano-coatings (options)
US20230279540A1 (en) Method of forming a diamond film
KR101718879B1 (en) Method of Manufacturing Electrode Having Controlled Work Function Using Functional Polymer Thin Film
CN109517345A (en) Poly- 3- hexyl thiophene material of a kind of carbon nanotube bonding and preparation method thereof
JPH07232399A (en) Formation of fluoroplastic film
WO2008046398A2 (en) Method for producing self-assembled monolayers on solid body surfaces
Yeliz et al. Rare Earth Element Doped ZnO Thin Films and Applications
JP2005125169A (en) Surface treating method

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 17850150

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 17850150

Country of ref document: EP

Kind code of ref document: A1