WO2018223752A1 - 复合电极、使用其的声学传感器及制造方法 - Google Patents

复合电极、使用其的声学传感器及制造方法 Download PDF

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WO2018223752A1
WO2018223752A1 PCT/CN2018/080653 CN2018080653W WO2018223752A1 WO 2018223752 A1 WO2018223752 A1 WO 2018223752A1 CN 2018080653 W CN2018080653 W CN 2018080653W WO 2018223752 A1 WO2018223752 A1 WO 2018223752A1
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composite electrode
layer
acoustic sensor
polymer
substrate
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English (en)
French (fr)
Inventor
彭锐
王庆贺
万想
高昕伟
王欣欣
范招康
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BOE Technology Group Co Ltd
Hefei Xinsheng Optoelectronics Technology Co Ltd
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BOE Technology Group Co Ltd
Hefei Xinsheng Optoelectronics Technology Co Ltd
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Priority to US16/305,229 priority Critical patent/US11082788B2/en
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    • H—ELECTRICITY
    • H04—ELECTRIC COMMUNICATION TECHNIQUE
    • H04R—LOUDSPEAKERS, MICROPHONES, GRAMOPHONE PICK-UPS OR LIKE ACOUSTIC ELECTROMECHANICAL TRANSDUCERS; ELECTRIC HEARING AIDS; PUBLIC ADDRESS SYSTEMS
    • H04R31/00—Apparatus or processes specially adapted for the manufacture of transducers or diaphragms therefor
    • H04R31/003—Apparatus or processes specially adapted for the manufacture of transducers or diaphragms therefor for diaphragms or their outer suspension
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01H—MEASUREMENT OF MECHANICAL VIBRATIONS OR ULTRASONIC, SONIC OR INFRASONIC WAVES
    • G01H9/00—Measuring mechanical vibrations or ultrasonic, sonic or infrasonic waves by using radiation-sensitive means, e.g. optical means
    • H—ELECTRICITY
    • H04—ELECTRIC COMMUNICATION TECHNIQUE
    • H04R—LOUDSPEAKERS, MICROPHONES, GRAMOPHONE PICK-UPS OR LIKE ACOUSTIC ELECTROMECHANICAL TRANSDUCERS; ELECTRIC HEARING AIDS; PUBLIC ADDRESS SYSTEMS
    • H04R31/00—Apparatus or processes specially adapted for the manufacture of transducers or diaphragms therefor
    • H—ELECTRICITY
    • H04—ELECTRIC COMMUNICATION TECHNIQUE
    • H04R—LOUDSPEAKERS, MICROPHONES, GRAMOPHONE PICK-UPS OR LIKE ACOUSTIC ELECTROMECHANICAL TRANSDUCERS; ELECTRIC HEARING AIDS; PUBLIC ADDRESS SYSTEMS
    • H04R19/00—Electrostatic transducers
    • H04R19/005—Electrostatic transducers using semiconductor materials
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10—Organic polymers or oligomers
    • H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
    • H10K85/113—Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10—Organic polymers or oligomers
    • H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
    • H10K85/115—Polyfluorene; Derivatives thereof
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N30/00—Piezoelectric or electrostrictive devices
    • H10N30/01—Manufacture or treatment
    • H10N30/09—Forming piezoelectric or electrostrictive materials
    • H10N30/098—Forming organic materials
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N30/00—Piezoelectric or electrostrictive devices
    • H10N30/30—Piezoelectric or electrostrictive devices with mechanical input and electrical output, e.g. functioning as generators or sensors
    • H10N30/302—Sensors
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N30/00—Piezoelectric or electrostrictive devices
    • H10N30/80—Constructional details
    • H10N30/85—Piezoelectric or electrostrictive active materials
    • H10N30/857—Macromolecular compositions
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N39/00—Integrated devices, or assemblies of multiple devices, comprising at least one piezoelectric, electrostrictive or magnetostrictive element covered by groups H10N30/00 – H10N35/00
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01V—GEOPHYSICS; GRAVITATIONAL MEASUREMENTS; DETECTING MASSES OR OBJECTS; TAGS
    • G01V1/00—Seismology; Seismic or acoustic prospecting or detecting
    • G01V1/01—Measuring or predicting earthquakes
    • H—ELECTRICITY
    • H04—ELECTRIC COMMUNICATION TECHNIQUE
    • H04R—LOUDSPEAKERS, MICROPHONES, GRAMOPHONE PICK-UPS OR LIKE ACOUSTIC ELECTROMECHANICAL TRANSDUCERS; ELECTRIC HEARING AIDS; PUBLIC ADDRESS SYSTEMS
    • H04R2231/00—Details of apparatus or processes specially adapted for the manufacture of transducers or diaphragms therefor covered by H04R31/00, not provided for in its subgroups
    • H04R2231/003—Manufacturing aspects of the outer suspension of loudspeaker or microphone diaphragms or of their connecting aspects to said diaphragms
    • 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
    • H10K71/60—Forming conductive regions or layers, e.g. electrodes

Definitions

  • the present disclosure relates to the field of acoustic sensors and display, and in particular to a composite electrode, an acoustic sensor using the same, and a method of manufacturing a composite electrode.
  • OLED Organic Light-Emitting Diode
  • OLED Organic Light-Emitting Diode
  • An acoustic sensor/sound sensor which may also be referred to as an acoustic sensor, is a device or device that converts mechanical vibrations propagating in a gaseous liquid or solid into electrical signals. It detects the signal in a contact or non-contact manner.
  • acoustic sensors There are many types of acoustic sensors, which can be divided into piezoelectric, electrostrictive, electromagnetic, electrostatic, and magnetostrictive according to the measurement principle.
  • the OLED device is combined with the sensor to form an OLED acoustic sensor. It is a technical problem to be solved by the present disclosure.
  • An object of the present disclosure is to provide a composite electrode, an acoustic sensor using the same, and a manufacturing method, which combines an OLED device and a sensor by using OLED characteristics to form an OLED acoustic sensor.
  • a composite electrode comprising: a conductive layer; a semiconductor high molecular polymer layer having a three-dimensional mesh structure formed on the conductive layer.
  • the conductive layer is a polyethylene dioxythiophene-poly(styrenesulfonic acid) PEDOT:PSS layer.
  • the semiconductor high molecular polymer is a hole/electron injection function material or a bipolar material.
  • the material of the hole/electron injection function is a polyfluorene derivative.
  • the bipolar material is PBTPBF-BT.
  • a method of fabricating a composite electrode includes: preparing a conductive layer; coating a solution of a mixture of a semiconductor high molecular polymer and a small molecule polymer on the conductive layer, and curing by forming a uniform film; a good solvent for coating the small molecule polymer on the uniform film; spin coating the uniform film to pour the dissolved small molecule polymer out of the uniform film to form a three-dimensional mesh structure Semiconductor polymer layer.
  • the small molecule polymer is polybutyl acrylate, polybutyl acrylate or polymethyl methacrylate.
  • the semiconductor high molecular polymer content is 20% by weight to 60% by weight in the mixture of the semiconductor high molecular polymer and the small molecule polymer.
  • the good solvent of the small molecule polymer is acetone, isopropanol or ethyl acetate polar solvent.
  • an acoustic sensor comprising: a substrate; the aforementioned composite electrode formed on the substrate; an organic layer formed on the composite electrode; and a top formed on the organic layer electrode.
  • the acoustic sensor further includes a flat layer formed between the composite electrode and the organic layer.
  • the material of the substrate is polyethylene terephthalate (PET).
  • the organic layer includes a hole/electron transport layer and an electroluminescent layer.
  • an acoustic sensor array comprising: a substrate; a plurality of the aforementioned acoustic sensors arranged in an array on the substrate.
  • the substrate is a flexible substrate.
  • vibration of the sound causes a change in current, so that the current of the OLED device changes, the area of the exciton recombination changes, and the color of the OLED emits light. Variety. Changes in sound intensity and changes in the frequency of sound waves cause changes in the color of the OLED device, which can be used for sound detection and monitoring of seismic waves in the natural environment.
  • a good solvent of a small molecule polymer is coated on a uniform film formed of a mixture of a semiconductor high molecular polymer and a small molecule polymer, and the uniform film is spin coated to dissolve The small molecule polymer scoops out the uniform film to form a semiconductor high molecular polymer layer having a three-dimensional mesh structure.
  • the above coating method is a blade coating.
  • the OLED acoustic sensor of the present disclosure can be flexibly utilized for flexible electronic and electronic skin directions, utilizing the light weight and flexibility characteristics of the OLED itself.
  • FIG. 1 shows a schematic view of a composite electrode in accordance with an example embodiment of the present disclosure.
  • FIG. 2 illustrates a three-dimensional mesh structure diagram of a semiconductor high molecular polymer layer in a composite electrode according to an example embodiment of the present disclosure.
  • FIG. 3 illustrates a flow chart of a method of fabricating a composite electrode in accordance with an example embodiment of the present disclosure.
  • FIG. 4 shows a schematic diagram of an acoustic sensor in accordance with an example embodiment of the present disclosure.
  • FIG. 5 shows a schematic diagram of an acoustic sensor array in accordance with an example embodiment of the present disclosure.
  • Example embodiments will now be described more fully with reference to the accompanying drawings.
  • the example embodiments can be embodied in a variety of forms, and should not be construed as being limited to the examples set forth herein; the described features, structures, or characteristics may be combined in any suitable manner in one or more embodiments.
  • numerous details are set forth to provide a However, one skilled in the art will appreciate that one or more of the specific details may be omitted or other methods, components, devices, steps, etc. may be employed.
  • An object of the present disclosure is to provide a composite electrode, an acoustic sensor using the composite electrode, and a method of manufacturing the composite electrode.
  • the OLED device is combined with the sensor to form an OLED acoustic sensor.
  • the composite electrode includes: a conductive layer; a semiconductor high molecular polymer layer having a three-dimensional mesh structure formed on the conductive layer.
  • the acoustic sensor includes: a substrate; the aforementioned composite electrode formed on the substrate; an organic layer formed on the composite electrode; and a top electrode formed on the organic layer.
  • the vibration of the sound causes a change in current, so that the current of the OLED device changes, the area of the exciton recombination changes, the color of the OLED emits light, the sound intensity changes, and the acoustic vibration
  • the change in frequency causes the color of the OLED device to change, which can be set for sound detection and monitoring of seismic waves in the natural environment; in addition, by coating on a uniform film formed by a mixture of a semiconductor polymer and a small molecule polymer A good solvent for the small molecule polymer is coated, and then the uniform film is spin-coated to separate the dissolved small molecule polymer into a uniform film to form a semiconductor polymer layer having a three-dimensional mesh structure.
  • FIG. 1 shows a schematic view of a composite electrode according to an exemplary embodiment of the present disclosure
  • FIG. 2 illustrates a semiconductor in a composite electrode according to an exemplary embodiment of the present disclosure.
  • the composite electrode 100 includes a conductive layer 2 and a semiconductor high molecular polymer layer 3 having a three-dimensional mesh structure formed on the conductive layer 2.
  • the three-dimensional mesh structure of the semiconductor polymer layer 3 is shown in FIG. 2.
  • FIG. 2 shows a partial microscopic enlarged view of a three-dimensional square structure of a 2 micron square structure, which contains many semiconductor polymer polymerizations.
  • the thin line of the object, the vibration of the sound causes the vibration of the thin wire, so that the current passing through the thin wire changes, thereby realizing the sensing of the sound.
  • the composite electrode of the present disclosure is not limited to the realization of sound sensing, and any form of motion or energy that can cause vibration of the thin wire causes a change in current through the thin wire to be sensed. .
  • the conductive layer is a polyethylene dioxythiophene-poly(styrenesulfonic acid) (PEDOT:PSS) layer.
  • PEDOT:PSS polyethylene dioxythiophene-poly(styrenesulfonic acid)
  • the semiconductor high molecular polymer is a hole/electron injection function material or a bipolar material.
  • the material of the hole/electron injection function is a polyfluorene derivative, for example, may be published [Zhu R, Wen G A, et al, Macromol Rapid Commun, 2005, 26 Polyfluorene (PF) derivatives reported in 1729].
  • the bipolar material may be PBTPBF- reported in the publication [Zhang, Guobing; Ye, Zhiwei; et al, Polymer chemistry, 2015, 6(21), 3970-3978].
  • FIG. 3 illustrates a flow chart of a method of fabricating a composite electrode in accordance with an example embodiment of the present disclosure.
  • a conductive layer is prepared.
  • the conductive layer can be prepared on the substrate 1 (see Fig. 1) by applying a layer of PEDOT:PSS (if coated by PEDOT:PSS), after curing treatment; the curing temperature is 120 ° C for the time 10-15min.
  • the substrate 1 may be composed of polyethylene terephthalate (PET), but is not limited thereto.
  • a solution of a mixture of a semiconductor high molecular polymer and a small molecule polymer is coated on the conductive layer, and cured to form a uniform film.
  • the semiconductor high molecular polymer may be a hole/electron injection function material or a bipolar material.
  • the material of the hole/electron injection function may be a polyfluorene derivative, which may be published [Zhu R, Wen G A, et al, Macromol Rapid Commun, 2005, 26: Polyfluorene (PF) derivatives reported in 1729].
  • the bipolar material may be PBTPBF- reported in the publication [Zhang, Guobing; Ye, Zhiwei; et al, Polymer chemistry, 2015, 6(21), 3970-3978].
  • the molecular weight of the small molecule polymer is selected to be between 2000 and 3000, and the small molecule polymer may be polybutyl acrylate (PBA), polybutyl acrylate (PtBA) or polymethyl methacrylate (PMMA).
  • PBA polybutyl acrylate
  • PtBA polybutyl acrylate
  • PMMA polymethyl methacrylate
  • a good solvent for the small molecule polymer such as by knife coating, is applied to the uniform film.
  • the solvent may be acetone, isopropanol or ethyl acetate polar solvent, which is a benign solvent for small molecule polymers, and has poor solubility to high molecular polymers.
  • the uniform film is spin-coated, and the dissolved small molecule polymer is extracted into a uniform film to form a semiconductor high molecular polymer layer having a three-dimensional mesh structure.
  • a three-dimensional semiconductor high molecular polymer mesh structure is formed, and the three-dimensional mesh structure contains a plurality of thin semiconductor polymer thin wires (refer to FIG. 2), wherein the fine line thickness of the mesh structure can be high.
  • the ratio of the molecular polymer to the small molecule polymer is controlled, wherein the ratio of the small molecule polymer: high molecular polymer is adjusted between 20% and 60% by weight, and the thickness of the fine line determines the sensitivity of the sensor.
  • FIG. 4 shows a schematic diagram of an acoustic sensor in accordance with an example embodiment of the present disclosure.
  • the acoustic sensor 400 includes: a substrate 1; a composite electrode 100 according to the foregoing embodiment formed on a substrate, comprising a conductive layer 2 and a semiconductor polymer layer 3 having a three-dimensional mesh structure; An organic layer 5 formed on the composite electrode; and a top electrode 6 formed on the organic layer 5.
  • the preparation of the substrate 1 and the composite electrode 100 is the same as the foregoing embodiment, and details are not described herein again.
  • the acoustic sensor further includes a flat layer 4 formed between the composite electrode 100 and the organic layer 5.
  • the preparation process of the flat layer is as follows: firstly, a silicon substrate is prepared, and then a micro hole is etched for a surface of the silicon substrate, wherein the micropore has a depth of 50-100 nm and a diameter of 40-100 nm, and the silicon substrate passes through octadecyl three.
  • PEDOT:PSS transfer layer is fabricated on the silicon substrate, that is, a layer of PEDOT:PSS is coated on the surface of the silicon substrate having micropores, and the temperature is 120 ° C
  • the film is cured at a time of 10-15 minutes to prepare a layer of PEDOT:PSS film having a convex bottom; and finally, the three-dimensional semiconductor polymer layer 3 of the composite electrode 100 is transferred to the composite PEDOT:PSS film layer.
  • the surface of the mesh structure is arranged to increase interfacial contact with the three-dimensional mesh structure and to increase electrical conductivity. It should be particularly noted here that the flat layer is not required for the acoustic sensor of the present disclosure, but is a preferred embodiment.
  • an organic layer 5 and an electrode layer 6 are prepared on the flat layer 4 (or the semiconductor high polymer layer 3) to finally obtain an OLED acoustic sensor.
  • the organic layer 5 may comprise a hole/electron transport layer and an electroluminescent layer, ie an EML layer
  • the hole transport layer may be NPB
  • the electroluminescent layer, ie the EML layer may be NPB:Rubrene
  • the hole transport layer is BCP.
  • the electroluminescent layer, ie the EML layer is BCP: DCJTB.
  • the electron/hole and EML layer materials of the OLED acoustic sensor satisfy the current change through the OLED device, the carrier recombination region changes, and the OLED luminescence color changes.
  • the OLED acoustic sensor of the present embodiment utilizes a composite electrode including a three-dimensional mesh structure, and the vibration of the sound causes a change in current, so that the current of the OLED device changes, the area of the exciton recombination changes, and the color of the OLED emits light. Variety. Due to changes in sound intensity and changes in the acoustic vibration frequency, the color of the OLED device also changes, which can be used for sound detection and monitoring of seismic waves in the natural environment. When the vibration of the sound disappears, the OLED device returns to its original state and can be recycled. At the same time, due to the light weight and flexibility of the OLED device itself, the OLED acoustic sensor can be flexibly applied to flexible electronic and electronic skin directions.
  • FIG. 5 shows a schematic diagram of an acoustic sensor array in accordance with an example embodiment of the present disclosure.
  • the acoustic sensor array 500 includes a substrate 7 and a plurality of acoustic sensors 400 as described in the foregoing embodiments arranged in an array on the substrate.
  • the substrate 7 is a flexible substrate.
  • the three-dimensional mesh structure in the foregoing embodiment is prepared on the composite electrode, but the three-dimensional mesh structure can also be prepared in the charge generation layer (CGL) of the OLED acoustic sensor, and the connection is set to be different.
  • the unit's OLED acoustic sensor is prepared on the composite electrode, but the three-dimensional mesh structure can also be prepared in the charge generation layer (CGL) of the OLED acoustic sensor, and the connection is set to be different.
  • the composite electrode, the acoustic sensor using the same, and the method of manufacturing according to embodiments of the present disclosure have one or more of the following advantages.
  • vibration of the sound causes a change in current, so that the current of the OLED device changes, the area of the exciton recombination changes, and the color of the OLED emits light. Variety.
  • the change in sound intensity and the change in the frequency of the acoustic vibration cause the color of the OLED device to change, which can be set for sound detection and monitoring of seismic waves in the natural environment.
  • a small solvent is coated on a uniform film formed of a mixture of a semiconductor high molecular polymer and a small molecule polymer, and then the uniform film is spin coated to dissolve small
  • the molecular polymer extracts a uniform film to form a semiconductor high molecular polymer layer having a three-dimensional mesh structure.
  • the OLED acoustic sensor of the present disclosure may be flexible using the light weight and flexibility characteristics of the OLED itself, and may be configured as a flexible electronic and electronic skin direction.

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  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Acoustics & Sound (AREA)
  • Signal Processing (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • General Physics & Mathematics (AREA)
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  • Electroluminescent Light Sources (AREA)
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Abstract

本公开提供一种复合电极、使用其的声学传感器及制造方法。复合电极包括：导电层；形成在所述导电层上的具有三维网孔结构的半导体高分子聚合物层。声学传感器包括：基底；形成在所述基底上的前述的复合电极；形成在所述复合电极上的有机层；形成在所述有机层上的顶电极。利用三维网孔结构作为复合电极，声音的振动会引起电流的变化，从而通过OLED器件的电流改变，激子复合的区域发生改变，OLED发光的颜色也会发生变化。声音强度的变化以及声波振动频率的变化，导致OLED器件的颜色也随之发生改变，可用于声音检测以及自然环境中地震波的监测。

Description

复合电极、使用其的声学传感器及制造方法
交叉引用
本公开要求于2017年6月9日递交的中国专利申请第201710431845.X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。
技术领域
本公开涉及声学传感器及显示领域，具体而言，涉及一种复合电极、使用该复合电极的声学传感器及复合电极制造方法。
背景技术
OLED(Organic Light-Emitting Diode,有机发光二极管)是近年来逐渐发展起来的显示照明技术，尤其在显示行业，是当今平板显示器研究领域的热点之一，与液晶显示器相比，由于其具有高响应、高对比度、低工作电压，轻薄，可柔性化、低能耗、生产成本低、自发光、宽视角及响应速度快等优点，目前，在手机、PDA、数码相机等显示领域OLED已经开始取代传统的LCD显示屏，被视为拥有广泛的应用前景，具有重要的研究意义。根据OLED器件的出光方向，可分为底发射OLED器件和顶发射OLED器件。
声学传感器/声音传感器又可称之为声敏传感器，它是一种在气体液体或固体中传播的机械振动转换成电信号的器件或装置。它用接触或非接触的方式检测信号。声敏传感器的种类很多，按测量原理可分为压电、电致伸缩效应、电磁感应、静电效应和磁致伸缩等。
利用OLED特点，将OLED器件与传感器结合，制成OLED声学传感器。是本公开要解决的技术问题。
在所述背景技术部分公开的上述信息仅用于加强对本公开的背景的理解，因此它可以包括不构成对本领域普通技术人员已知的相关技术的信息。
发明内容
本公开的目的在于提供一种复合电极、使用其的声学传感器及制造方法，利用OLED特点，将OLED器件与传感器结合，制成OLED声学传感器。
本公开的其他特性和优点将通过下面的详细描述变得清晰，或者部分地通过本公开的实践而习得。
根据本公开的第一方面，公开一种复合电极，包括：导电层；形成在所述导电层上的具有三维网孔结构的半导体高分子聚合物层。
在本公开的一示例性实施方式中，所述导电层为聚乙撑二氧噻吩-聚(苯乙烯磺酸)PEDOT:PSS层。
在本公开的一示例性实施方式中，所述半导体高分子聚合物为空穴/电子注入功能的材料或者双极性材料。
在本公开的一示例性实施方式中，所述空穴/电子注入功能的材料为聚芴类衍生物。
在本公开的一示例性实施方式中，所述双极性材料为PBTPBF-BT。
根据本公开的第二方面，公开一种复合电极的制造方法，包括：制备导电层；在所述导电层上涂覆半导体高分子聚合物和小分子聚合物的混合物的溶液，经固化处理形成均一膜；在所述均一膜上涂覆小分子聚合物的良溶剂；对所述均一膜进行旋凃，将溶解的小分子聚合物甩出所述均一膜，从而形成具有三维网孔结构的半导体高分子聚合物层。
在本公开的一示例性实施方式中，所述小分子聚合物为聚丙烯酸丁酯、聚丙烯酸异丁酯或聚甲基丙烯酸甲酯。
在本公开的一示例性实施方式中，在所述半导体高分子聚合物和小分子聚合物的混合物中半导体高分子聚合物含量为20wt％-60wt％。
在本公开的一示例性实施方式中，所述小分子聚合物的良溶剂为丙酮、异丙醇或乙酸乙酯极性溶剂。
根据本公开的第三方面，公开一种声学传感器，包括：基底；形成在所述基底上的前述的复合电极；形成在所述复合电极上的有机层；形成在所述有机层上的顶电极。
在本公开的一示例性实施方式中，所述声学传感器还包括形成在所述复合电极和所述有机层之间的平坦层。
在本公开的一示例性实施方式中，所述基底的材料为聚对苯二甲酸乙二醇酯(PET)。
在本公开的一示例性实施方式中，所述有机层包括空穴/电子传输层和电致发光层。
根据本公开的第四方面，公开一种声学传感器阵列，包括：基板；在所述基板上呈阵列排布的多个前述的声学传感器。
在本公开的一示例性实施方式中，所述基板为柔性基板。
根据本公开的一些实施方式，通过利用三维网孔结构作为复合电极，声音的振动会引起电流的变化，从而通过OLED器件的电流改变，激子复合的区域发生改变，OLED发光的颜色也会发生变化。声音强度的变化以及声波振动频率的变化，导致OLED器件的颜色也随之发生改变，可用于声音检测以及自然环境中地震波的监测。
根据本公开的一些实施方式，通过在由半导体高分子聚合物和小分子聚合物的混合物形成的均一膜上涂覆小分子聚合物的良溶剂，然对所述均一膜进行旋凃，将溶解的小分子聚合物甩出所述均一膜，从而形成具有三维网孔结构的半导体高分子聚合物层。
根据本公开的一些实施方式，上述涂覆方式为刮涂。
根据本公开的一些实施方式，利用OLED本身的质轻以及柔性的特点，本公开的OLED声学传感器可以柔性化，可应用于柔性电子以及电子皮肤方向。
应当理解的是，以上的一般描述和后文的细节描述仅是示例性和解释性的，并不能限制本公开。
附图说明
通过参照附图详细描述其示例实施例，本公开的上述和其它目标、特征及优点将变得更 加显而易见。
此处的附图被并入说明书中并构成本说明书的一部分，示出了符合本公开的实施例，并与说明书一起用于解释本公开的原理。下面描述中的附图仅仅是本公开的一些实施例，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其他的附图。
图1示出根据本公开一示例实施方式的复合电极的示意图。
图2示出根据本公开一示例实施方式的复合电极中的半导体高分子聚合物层的三维网孔结构图。
图3示出根据本公开一示例实施方式的复合电极的制造方法的流程图。
图4示出根据本公开一示例实施方式的声学传感器的示意图。
图5示出根据本公开一示例实施方式的声学传感器阵列的示意图。
具体实施方式
现在将参考附图更全面地描述示例实施方式。然而，示例实施方式能够以多种形式实施，且不应被理解为限于在此阐述的范例；所描述的特征、结构或特性可以以任何合适的方式结合在一个或更多实施方式中。在下面的描述中，提供许多细节从而给出对本公开的实施方式的充分理解。然而，本领域技术人员将意识到，可以实践本公开的技术方案而省略所述特定细节中的一个或更多，或者可以采用其它的方法、组元、装置、步骤等。
需要指出的是，在附图中，为了图示的清晰可能会夸大层和区域的尺寸。而且可以理解，当元件或层被称为在另一元件或层“上”时，它可以直接在其他元件上，或者可以存在中间的层。另外，可以理解，当元件或层被称为在另一元件或层“下”时，它可以直接在其他元件下，或者可以存在一个以上的中间的层或元件。另外，还可以理解，当层或元件被称为在两层或两个元件“之间”时，它可以为两层或两个元件之间唯一的层，或还可以存在一个以上的中间层或元件。通篇相似的参考标记指示相似的元件。
本公开的目的在于提供一种复合电极、使用该复合电极的声学传感器及复合电极的制造方法。利用OLED特点，将OLED器件与传感器结合，制成OLED声学传感器。复合电极包括：导电层；形成在导电层上的具有三维网孔结构的半导体高分子聚合物层。声学传感器包括：基底；形成在基底上的前述的复合电极；形成在复合电极上的有机层；形成在有机层上的顶电极。利用三维网孔结构作为复合电极，声音的振动会引起电流的变化，从而通过OLED器件的电流改变，激子复合的区域发生改变，OLED发光的颜色也会发生变化，声音强度的变化以及声波振动频率的变化导致OLED器件的颜色也随之发生改变，可设置为声音检测以及自然环境中地震波的监测；此外，通过在由半导体高分子聚合物和小分子聚合物的混合物形成的均一膜上涂覆小分子聚合物的良溶剂，然后， 对均一膜进行旋凃，将溶解的小分子聚合物甩出均一膜，从而形成具有三维网孔结构的半导体高分子聚合物层。
下面结合图1-2对本公开的复合电极进行说明，其中，图1示出根据本公开一示例实施方式的复合电极的示意图，图2示出根据本公开一示例实施方式的复合电极中的半导体高分子聚合物层的三维网孔结构图。
如图1所示，复合电极100包括导电层2和形成在导电层2上的具有三维网孔结构的半导体高分子聚合物层3。半导体高分子聚合物层3的三维网孔结构如图2所示，图2示出的是2微米见方的三维网孔结构局部显微放大图，三维网孔结构中包含很多的半导体高分子聚合物细线，声音的振动会引起细线的振动，从而通过细线的电流就会发生改变，从而实现声音的传感。在此需要特别指出的是，本公开的复合电极并不仅局限于实现声音的传感，任何能够引起细线的振动的运动形式或能量形式都会引起通过细线的电流发生改变从而被感测到。
在本公开的一示例性实施方式中，该导电层为聚乙撑二氧噻吩-聚(苯乙烯磺酸)(PEDOT:PSS)层。
在本公开的一示例性实施方式中，该半导体高分子聚合物为空穴/电子注入功能的材料或者双极性材料。
在本公开的一示例性实施方式中，空穴/电子注入功能的材料为聚芴类衍生物，例如，可为公开文献[Zhu R,Wen G A,et al,Macromol Rapid Commun,2005,26:1729]中报道的聚芴(PF)类衍生物。
在本公开的一示例性实施方式中，双极性材料可为公开文献[Zhang,Guobing；Ye,Zhiwei；et al,Polymer chemistry,2015,6(21),3970-3978]中报道的PBTPBF-BT。
图3示出根据本公开一示例实施方式的复合电极的制造方法的流程图。
如图3所示，在S302，制备导电层。导电层的制备可在基板1(参见图1)上，涂覆一层PEDOT:PSS(如采取刮涂的方式涂覆PEDOT:PSS)，经固化处理后形成；固化温度为120℃，时间为10-15min。举例来说，基板1可由聚对苯二甲酸乙二醇酯(PET)构成，但不限于此。
在S304，在导电层上涂覆半导体高分子聚合物和小分子聚合物的混合物的溶液，经固化处理形成均一膜。
在本公开的一示例性实施方式中，半导体高分子聚合物可以为空穴/电子注入功能的材料或者双极性材料。
在本公开的一示例性实施方式中，空穴/电子注入功能的材料可以为聚芴类衍生物，可为公开文献[Zhu R,Wen G A,et al,Macromol Rapid Commun,2005,26:1729]中 报道的聚芴(PF)类衍生物。
在本公开的一示例性实施方式中，双极性材料可为公开文献[Zhang,Guobing；Ye,Zhiwei；et al,Polymer chemistry,2015,6(21),3970-3978]中报道的PBTPBF-BT。
小分子聚合物的分子量选为在2000-3000之间，小分子聚合物可为聚丙烯酸丁酯(PBA)，聚丙烯酸异丁酯(PtBA)或聚甲基丙烯酸甲酯(PMMA)。
在S306，在均一膜上涂覆如，通过刮涂方式，小分子聚合物的良溶剂。其中溶剂可为丙酮、异丙醇，乙酸乙酯极性溶剂，为小分子聚合物的良性溶剂，对高分子聚合物溶解性较差。
在S308，对均一膜进行旋凃，将溶解的小分子聚合物甩出均一膜，从而形成具有三维网孔结构的半导体高分子聚合物层。
在完成前述的在均一膜上涂覆小分子聚合物的良溶剂的步骤后，经过一段时间的溶解，将出现相分离，接着对均一膜进行旋凃，将溶解的小分子甩出均一膜，在此过程中形成了三维的半导体高分子聚合物网孔结构，三维网孔结构中包含很多的半导体高分子聚合物细线(可继续参考图2)，其中网孔结构的细线粗细可由高分子聚合物与小分子聚合物的比例来控制，其中小分子聚合物：高分子聚合物的比例在20wt％-60wt％之间进行调节，细线的粗细可决定传感器的灵敏度。
下面结合图4对本公开的声学传感器进行说明。图4示出根据本公开一示例实施方式的声学传感器的示意图。
如图4所示，声学传感器400包括：基底1；形成在基底上的如前述实施方式所述的复合电极100，其包括导电层2和具有三维网孔结构的半导体高分子聚合物层3；形成在该复合电极上的有机层5；以及形成在有机层5上的顶电极6。
其中基底1和复合电极100的制备同前述实施方式，在此不再赘述。
在本公开的一示例性实施方式中，声学传感器还包括形成在复合电极100和有机层5之间的平坦层4。平坦层的制备过程如下：首先制备一硅基板，然后为硅基板的一表面刻蚀微孔，其中微孔的深度尺寸为50-100nm，直径为40-100nm，硅基板经过十八烷基三氯硅烷(OTS)处理，达到一定的疏液作用；接着在硅基板上制作PEDOT:PSS转印层，即在硅基板具有微孔的表面上涂覆一层PEDOT:PSS，经过温度为120℃，时间10-15min固化处理，制备一层底部有凸起的PEDOT:PSS膜层；最后将有凸起的PEDOT:PSS膜层转印至复合电极100中的半导体高分子聚合物层3的三维网孔结构的表面上，设置为增加与三维网孔结构的界面接触以及增加导电性能。在此需要特别指出的是，平坦层并不是本公开的声学传感器所必需的，只是优选的实施方式。
接着再在平坦层4(或半导体高分子聚合物层3)上制备有机层5和电极层6，最终制得OLED声学传感器。其中有机层5可包括空穴/电子传输层和电致发光层即EML层，空穴传输层可为NPB，电致发光层即EML层可为NPB:Rubrene，或空穴传输层为BCP而电致发光层即EML层为BCP：DCJTB。OLED声学传感器的电子/空穴和EML层材料满足通过OLED器件的电流变化，载流子复合区域改变，OLED发光颜色改变。
本实施方式的OLED声学传感器，利用包括三维网孔结构的复合电极，声音的振动会引起电流的变化，从而通过OLED器件的电流改变，激子复合的区域发生改变，OLED发光的颜色也会发生变化。由于声音强度的变化，和声波振动频率的变化，OLED器件的颜色也随之发生改变，可用于声音检测以及自然环境中地震波的监测。而当该声音的振动消失时，OLED器件恢复原状，从而可循环使用。同时由于OLED器件本身的质轻以及柔性的特点，该OLED声学传感器可以柔性化，可应用于柔性电子以及电子皮肤方向。
图5示出根据本公开一示例实施方式的声学传感器阵列的示意图。
如图5所示，声学传感器阵列500，包括：基板7；在基板上呈阵列排布的多个如前述实施方式所述的声学传感器400。
在本公开的一示例性实施方式中，基板7为柔性基板。
此外，还需要特别说明的是，前述实施方式中三维网孔结构制备均是在复合电极上，但是三维网孔结构也可制备在OLED声学传感器的电荷产生层(CGL)中，设置为连接不同单元的OLED声学传感器。
通过以上的详细描述，本领域的技术人员易于理解，根据本公开实施例的复合电极、使用其的声学传感器及制造方法具有以下优点中的一个或几个。
根据本公开的一些实施方式，通过利用三维网孔结构作为复合电极，声音的振动会引起电流的变化，从而通过OLED器件的电流改变，激子复合的区域发生改变，OLED发光的颜色也会发生变化。声音强度的变化以及声波振动频率的变化，导致OLED器件的颜色也随之发生改变，可设置为声音检测以及自然环境中地震波的监测。
根据本公开的一些实施方式，通过在由半导体高分子聚合物和小分子聚合物的混合物形成的均一膜上涂覆小分子聚合物的良溶剂，然后对均一膜进行旋凃，将溶解的小分子聚合物甩出均一膜，从而形成具有三维网孔结构的半导体高分子聚合物层。
根据本公开的一些实施方式，利用OLED本身的质轻以及柔性的特点，本公开的OLED声学传感器可以柔性化，可应设置为柔性电子以及电子皮肤方向。
本领域技术人员在考虑说明书及实践这里公开的发明后，将容易想到本公开的其它实施方案。本申请旨在涵盖本公开的任何变型、用途或者适应性变化，这些变型、用途 或者适应性变化遵循本公开的一般性原理并包括本公开未公开的本技术领域中的公知常识或惯用技术手段。说明书和实施例仅被视为示例性的，本公开的真正范围和精神由下面的权利要求指出。
应当理解的是，本公开并不局限于上面已经描述并在附图中示出的精确结构，并且可以在不脱离其范围进行各种修改和改变。本公开的范围仅由所附的权利要求来限制。

Claims (15)

  1. 一种复合电极，包括：
    导电层；
    形成在所述导电层上的具有三维网孔结构的半导体高分子聚合物层。
  2. 根据权利要求1所述的复合电极，其中，所述导电层为聚乙撑二氧噻吩-聚(苯乙烯磺酸)PEDOT:PSS层。
  3. 根据权利要求1或2所述的复合电极，其中，所述半导体高分子聚合物为空穴/电子注入功能的材料或者双极性材料。
  4. 根据权利要求3所述的复合电极，其中，所述空穴/电子注入功能的材料为聚芴类衍生物。
  5. 根据权利要求3所述的复合电极，其中，所述双极性材料为PBTPBF-BT。
  6. 一种复合电极的制造方法，包括：
    制备导电层；
    在所述导电层上涂覆半导体高分子聚合物和小分子聚合物的混合物的溶液，经固化处理形成均一膜；
    在所述均一膜上涂覆小分子聚合物的良溶剂；
    对所述均一膜进行旋凃，将溶解的小分子聚合物甩出所述均一膜，从而形成具有三维网孔结构的半导体高分子聚合物层。
  7. 根据权利要求6所述的制造方法，其中，所述小分子聚合物为聚丙烯酸丁酯、聚丙烯酸异丁酯或聚甲基丙烯酸甲酯。
  8. 根据权利要求6或7所述的制造方法，其中，在所述半导体高分子聚合物和小分子聚合物的混合物中半导体高分子聚合物含量为20wt％-60wt％。
  9. 根据权利要求6-8中任一项所述的制造方法，其中，所述小分子聚合物的良溶剂为丙酮、异丙醇或乙酸乙酯极性溶剂。
  10. 一种声学传感器，包括：
    基底；
    设置在所述基底上的根据权利要求1-5之一所述的复合电极；
    设置在所述复合电极上的有机层；
    设置在所述有机层上的顶电极。
  11. 根据权利要求10所述的声学传感器，其中，还包括设置在所述复合电极和所述有机层之间的平坦层。
  12. 根据权利要求10或11所述的声学传感器，其中，所述基底的材料为聚对苯二甲酸乙二醇酯PET。
  13. 根据权利要求10-12中任一项所述的声学传感器，其中，所述有机层包括空穴/电子传输层和电致发光层。
  14. 一种声学传感器阵列，包括：
    基板；
    在所述基板上呈阵列排布的多个根据权利要求10-13之一所述的声学传感器。
  15. 根据权利要求14所述的声学传感器阵列，其中，所述基板为柔性基板。
PCT/CN2018/080653 2017-06-09 2018-03-27 复合电极、使用其的声学传感器及制造方法 Ceased WO2018223752A1 (zh)

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