阅读说明：本技术 集发光、开关、颜色控制的电致发光四极管及其控制方法 (Electroluminescent tetrode integrating light emission, switch and color control and control method thereof ) 是由 孟鸿 纪君朋 杨标 张超红 赵长斌 陈经伟 蔡雨露 孟智敏 于 2021-06-01 设计创作，主要内容包括：本发明公开了一种集发光、开关、颜色控制的电致发光四极管及其控制方法,电致发光四极管包括：依次设置的电极层,发光层以及调制层；所述发光层包括：至少两个子发光层；所述电极层包括：至少两个电极,相邻两个电极相互间隔设置；其中,所述电极与所述子发光层一一对应设置,所述调制层用于控制各子发光层。通过将发光层分成至少两个子发光层,并将电极层分成至少两个间隔设置的电极,电极与子发光层一一对应,因此,可以通过调制层分别控制各子发光层,这些子发光层可以形成一个像素,也就是说,给调制层一个控制信号,就可以集成化控制各子发光层。(The invention discloses an electroluminescent tetrode integrating luminescence, switching and color control and a control method thereof, wherein the electroluminescent tetrode comprises the following components: the light emitting diode comprises an electrode layer, a light emitting layer and a modulation layer which are arranged in sequence; the light emitting layer includes: at least two sub-light emitting layers; the electrode layer includes: at least two electrodes, wherein the two adjacent electrodes are arranged at intervals; the electrodes are arranged in one-to-one correspondence with the sub-light emitting layers, and the modulation layer is used for controlling each sub-light emitting layer. By dividing the light-emitting layer into at least two sub-light-emitting layers and dividing the electrode layer into at least two electrodes arranged at intervals, the electrodes and the sub-light-emitting layers are in one-to-one correspondence, so that the sub-light-emitting layers can be controlled separately by the modulation layer and can form a pixel, that is, the sub-light-emitting layers can be controlled in an integrated manner by giving a control signal to the modulation layer.)

1. An integrated light, switching, color control electroluminescent tetrode, comprising: the light emitting diode comprises an electrode layer, a light emitting layer and a modulation layer which are arranged in sequence;

the light emitting layer includes: at least two sub-light emitting layers;

the electrode layer includes: at least two electrodes, wherein the two adjacent electrodes are arranged at intervals;

the electrodes are arranged in one-to-one correspondence with the sub-light emitting layers, and the modulation layer is used for controlling each sub-light emitting layer.

2. The integrated light, switching, color-controlling electroluminescent tetrode of claim 1, wherein the electroluminescent tetrode further comprises:

a first direct current blocking layer located between the electrode layer and the light emitting layer; and/or

And the second direct current blocking layer is positioned between the light emitting layer and the modulation layer.

3. The integrated light, switch, color control electroluminescent tetrode of claim 2, wherein the first dc blocking layer is a dielectric layer; the second direct current barrier layer adopts a dielectric layer.

4. The integrated light, switching, color control electroluminescent tetrode of claim 2, wherein the electroluminescent tetrode further comprises:

and a hole generation layer connected to the light emitting layer.

5. The collective light emitting, switching, color controlled electroluminescent tetrode of claim 4, wherein the hole generating layer is a stack or a doped structure.

6. The integrated light, switching, color control electroluminescent tetrode of claim 4, wherein the electroluminescent tetrode further comprises:

an electron transport layer connected to the light emitting layer;

an electron injection layer connected to the electron transport layer;

the electron transport layer and the hole generation layer are respectively positioned on two sides of the light emitting layer.

7. The integrated light, switching, color-controlling electroluminescent tetrode of claim 1, wherein the electroluminescent tetrode further comprises:

and a substrate connected to the modulation layer or the electrode layer.

8. An integrated light, switching, color controlled electroluminescent tetrode according to any of claims 1-7,

the light emitting colors of the sub light emitting layers are different; and/or

Each sub-light emitting layer is spiral, and each electrode is spiral; and/or

The modulation layer adopts an electronic conductor layer or an ion conductor layer.

9. A method of controlling an integrated light, switching, color controlled electroluminescent tetrode as claimed in any of claims 1 to 8, comprising the steps of:

applying a multiphase alternating current to each electrode respectively, and applying a control signal to the modulation layer so as to control the sub-luminescent layers corresponding to the electrodes to emit light respectively; wherein the number of phases of the multi-phase alternating current is the same as the number of the electrodes.

10. The method of claim 9, wherein the control signal comprises: the voltage of the high level is larger than the peak voltage of the multi-phase alternating current.

Technical Field

The invention relates to the technical field of electroluminescence, in particular to an electroluminescence tetrode integrating luminescence, switching and color control and a control method thereof.

Background

Full-color display units are important components of intelligent electronic devices, and therefore, like other electronic components, the display units are also in need of miniaturization, integration and intelligence. With the introduction of electronic device system level integration concepts, more and more multifunctional electronic devices are attracting interest.

On the other hand, organic electrons are considered to be the development direction of future flexible electrons. In recent years, research on organic transistors (OTFTs) has been significantly advanced, and active matrix Organic Light Emitting Diode (OLED) displays using organic transistors have been reported. In the widely used active matrix OLED (AM-OLED) technology, the whole screen for full-color display is composed of a plurality of pixels, each pixel includes three sub-pixels respectively emitting red, green, and blue light, and the pixels of the whole screen display color by adjusting the color ratios of the red, green, and blue sub-pixels. And the switch control of each sub-pixel point needs to be completed through at least one transistor.

In order to simplify the structure of the light emitting device, an Organic Light Emitting Transistor (OLET) combining a light emitting function of the OLED and a circuit modulation function of the OTFT is proposed. This technique is expected to realize a simplified organic active matrix display, and is also expected to improve a pixel aperture ratio, reduce power consumption, and the like, and has attracted much attention.

In the prior art, the color control logic of the pixel is complex, the red, green and blue light-emitting sub-pixels need to be controlled respectively, and integrated control cannot be performed through one signal.

Accordingly, the prior art is yet to be improved and developed.

Disclosure of Invention

The present invention is directed to a mold, a crucible and a crystal growing apparatus, which are provided to solve the above-mentioned problems of the prior art, and aims to solve the problem that the prior art cannot perform integrated control by using one signal.

The technical scheme adopted by the invention for solving the technical problem is as follows:

an integrated light, switching, color controlled electroluminescent tetrode, comprising: the light emitting diode comprises an electrode layer, a light emitting layer and a modulation layer which are arranged in sequence;

the light emitting layer includes: at least two sub-light emitting layers;

the electrode layer includes: at least two electrodes, wherein the two adjacent electrodes are arranged at intervals;

the electrodes are arranged in one-to-one correspondence with the sub-light emitting layers, and the modulation layer is used for controlling each sub-light emitting layer.

The electroluminescent tetrode integrating luminescence, switching and color control further comprises:

a first direct current blocking layer located between the electrode layer and the light emitting layer; and/or

And the second direct current blocking layer is positioned between the light emitting layer and the modulation layer.

The electroluminescent tetrode integrating luminescence, switching and color control is characterized in that the first direct current blocking layer adopts a dielectric layer; the second direct current barrier layer adopts a dielectric layer.

The electroluminescent tetrode integrating luminescence, switching and color control further comprises:

and a hole generation layer connected to the light emitting layer.

The electroluminescent tetrode integrating luminescence, switching and color control is characterized in that the hole generation layer is of a laminated layer or a doped structure.

The electroluminescent tetrode integrating luminescence, switching and color control further comprises:

an electron transport layer connected to the light emitting layer;

an electron injection layer connected to the electron transport layer;

the electron transport layer and the hole generation layer are respectively positioned on two sides of the light emitting layer.

The electroluminescent tetrode integrating luminescence, switching and color control further comprises:

and a substrate connected to the modulation layer or the electrode layer.

The electroluminescent tetrode integrating luminescence, switching and color control is characterized in that,

the light emitting colors of the sub light emitting layers are different; and/or

Each sub-light emitting layer is spiral, and each electrode is spiral; and/or

The modulation layer adopts an electronic conductor layer or an ion conductor layer.

A method of controlling an integrated light, switching, color controlled electroluminescent tetrode as claimed in any preceding claim, comprising the steps of:

applying a multiphase alternating current to each electrode respectively, and applying a control signal to the modulation layer so as to control the sub-luminescent layers corresponding to the electrodes to emit light respectively; wherein the number of phases of the multi-phase alternating current is the same as the number of the electrodes.

The control method of the integrated light emitting, switching and color control electroluminescent tetrode is characterized in that the control signal comprises: the voltage of the high level is larger than the peak voltage of the multi-phase alternating current.

Has the advantages that: by dividing the light-emitting layer into at least two sub-light-emitting layers and dividing the electrode layer into at least two electrodes arranged at intervals, the electrodes and the sub-light-emitting layers are in one-to-one correspondence, so that the sub-light-emitting layers can be controlled separately by the modulation layer and can form a pixel, that is, the sub-light-emitting layers can be controlled in an integrated manner by giving a control signal to the modulation layer.

Drawings

Fig. 1 is a schematic structural diagram of a device with a bottom-side direct-current blocking layer and a bottom-side positive structure, wherein the device is provided with a regulating electrode according to an embodiment of the present invention.

Fig. 2 is a schematic structural diagram of a device with a top-up structure having a bottom dc blocking layer and a tuning electrode according to an embodiment of the present invention.

Fig. 3 is a schematic structural diagram of a device with a top-dc-blocking layer and a bottom-facing structure, which is provided by the embodiment of the present invention.

Fig. 4 is a schematic structural diagram of a device in which a modulation electrode is on a top dc blocking layer and is in a top-up structure according to an embodiment of the present invention.

Fig. 5 is a schematic structural diagram of a device with a bottom-direct current blocking layer on a bottom inverted structure and a tuning electrode according to an embodiment of the present invention.

Fig. 6 is a schematic structural diagram of a device with a bottom dc blocking layer and a top inverted structure as a tuning electrode according to an embodiment of the present invention.

Fig. 7 is a schematic structural diagram of a device with a top-dc-barrier-layer-on-bottom inverted structure and a tuning electrode according to an embodiment of the present invention.

Fig. 8 is a schematic structural diagram of a device with a top-inverted structure of a top dc blocking layer on a tuning electrode according to an embodiment of the present invention.

Fig. 9 is a schematic structural diagram of a device with a positive structure in which the adjustment electrode is disposed on the bottom dc blocking layer and on the top of the bottom dc blocking layer according to an embodiment of the present invention.

Fig. 10 is a schematic structural diagram of an upright structure device with a tuning electrode without a dc blocking layer on the bottom according to an embodiment of the present invention.

Fig. 11 is a schematic view of an interdigital electrode suitable for a three-phase electronic device electrode in example 1 of the present invention.

Fig. 12A to 12J are structural diagrams of an organic material used in a device manufacturing process in example 1 of the present invention.

Fig. 13 is a schematic structural diagram of an electroluminescent tetrode in embodiment 1 of the invention.

Fig. 14 is a schematic diagram of control signals represented by representative 8 control codes and corresponding driving signals in embodiment 1 of the present invention.

Fig. 15 is a distribution of the device light emission color states represented by all 64 control codes in CIE coordinates in example 1 of the present invention.

Description of reference numerals:

1. a substrate; 2. a modulation layer; 3. a direct current blocking layer; 4. a hole generating layer; 5. a light emitting layer; 5-1, a sub-luminescent layer; 5-2, a sub-luminescent layer; 5-3, a sub-luminescent layer; 6. an electron transport layer; 7. an electron injection layer; 8. an electrode layer; 8-1, electrodes; 8-2, electrodes; 8-3, and electrodes.

Detailed Description

In order to make the objects, technical solutions and advantages of the present invention clearer and clearer, the present invention is further described in detail below with reference to the accompanying drawings and examples. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.

Referring to fig. 1-15, the present invention provides some embodiments of an electroluminescent tetrode with integrated light emission, switching, and color control.

The inventors have found that Organic Light Emitting Transistors (OLETs) still currently have at least one or more of the following improvements:

(1) the luminous color cannot be adjusted or can be adjusted only within a small range. The present OLET technology can only realize emission and control of monochromatic light, and in order to realize further systematic integration, a desired technology should satisfy that one device simultaneously emits light of three colors of red, green, and blue, without subdividing a pixel point into three sub-pixels of red, green, and blue.

(2) The light emission color and the light emission luminance cannot be independently adjusted.

(3) The driving circuit and the control circuit are complicated. In the prior art, direct current or single-phase alternating current is mostly adopted to drive the light-emitting unit, and a driving circuit needs complex rear-end equipment to realize alternating current-direct current (AD) conversion, so that the static power loss is increased, the complexity of an integrated circuit is increased, and the aperture ratio is possibly reduced.

(4) The pixel color control logic is complex, can not be controlled by integration through a signal, and needs to control the red, green and blue light-emitting sub-pixels respectively, so that the storage and extraction of colors are not convenient.

The invention divides the luminous layer into at least two sub-luminous layers, and divides the electrode layer into at least two electrodes which are arranged at intervals, and the electrodes correspond to the sub-luminous layers one by one, therefore, the sub-luminous layers can be respectively controlled by the modulation layer, and the sub-luminous layers can form a pixel, namely, the sub-luminous layers can be controlled in an integrated way by giving a control signal to the modulation layer.

As shown in fig. 1-10, an integrated light emitting, switching, and color control electroluminescent tetrode of the present invention comprises:

an electrode layer 8, a light-emitting layer 5, and a modulation layer 2 provided in this order;

the light-emitting layer 5 includes: at least two sub-luminescent layers (5-1, 5-2, 5-3);

the electrode layer 8 includes: at least two electrodes (8-1, 8-2, 8-3), two adjacent electrodes (8-1, 8-2, 8-3) are arranged at intervals;

wherein the electrodes (8-1, 8-2, 8-3) are arranged in one-to-one correspondence with the sub-luminescent layers, and the modulation layer 2 is used for controlling each sub-luminescent layer (5-1, 5-2, 5-3).

It should be noted that the sub-emitting layers may use the same or different light-emitting materials, that is, the sub-emitting layers may emit the same light or different lights. In order for a single pixel to emit white light, the pixel typically includes at least three sub-pixels, which emit different light and may mix to form white light. Therefore, in order to make the light emitting layer emit white light, the light emitting layer includes at least three sub-light emitting layers, and the light emitted by the three sub-light emitting layers is mixed to form white light. The modulation layer is connected with a modulation signal, so that the overall switching and color change of the light-emitting device comprising the sub-light-emitting layers with different colors can be controlled, namely, the modulation layer can control the switching and light-emitting brightness of each sub-light-emitting layer, and the switching and color of the whole light-emitting layer can be adjusted.

Specifically, the operation principle is described by taking three sub-light emitting layers as an example:

the electroluminescent tetrode (i.e., the device) is driven by three-phase alternating current, and three sine wave output voltages of appropriate amplitude, which are 120 degrees out of phase with each other, are applied to the electrode 8-1, the electrode 8-2, and the electrode 8-3 in the electrode layer 8 of the device, respectively. At this time, if the control signal is not applied to the modulation layer, the red, green and blue light emitting cells all emit light. If a control signal is applied to the modulation layer, the red, green and blue light-emitting units of the device can be integrally controlled to have different light-emitting states, such as only red light, only green light, only blue light, red light and green light which are simultaneously bright, red light and blue light which are simultaneously bright, green light and blue light which are simultaneously bright, red, green and blue light-emitting units which are not bright, or red, green and blue light-emitting units which are all luminous but have different luminous brightness ratios. The interdigital electrode device is prepared by utilizing the principle, if the interdigital electrode distance is smaller than the resolution of human eyes, the adjustment of emergent light among red light, green light and blue light can be realized, and the adjustment range can cover a plane area of CIE coordinates.

The embodiment has the following advantages: in the embodiment, the color-adjustable organic electroluminescent tetrode is prepared by the way that the three different color light-emitting units are transversely arranged in parallel. The device can realize that three-phase alternating current drives to emit three colors of light, meets the requirement of direct connection to a power grid to realize plug and play, controls the luminous intensity of three luminous units through a control signal, can also control the proportion of three different colors of light, and realizes color regulation and control. The device integrates the functions of light emitting, switching and three-dimensional color control in a system level, is expected to simplify the preparation process and cost of a pixel structure, miniaturize a pixel unit, reduce the use of a TFT switching device and increase the aperture ratio.

The organic electroluminescent tetrode is prepared by using materials which are easy to commercialize, has simple preparation process, and is easy to form pixel points in a display.

The electroluminescent tetrode can adopt materials related to LEDs (including inorganic LEDs, organic LEDs, polymer LEDs, quantum dot LEDs, perovskite LEDs and the like), namely, the existing LED luminous layer can be used as the luminous layer of the electroluminescent tetrode, and the electrode layer of the existing LED can be used as the electrode layer of the electroluminescent tetrode. Of course, other functional layers of the LED, such as a hole transport layer, a hole injection layer, an electron transport layer, an electron injection layer, etc., can also be applied to the electroluminescent tetrode of the present application. Of course, the material of the electroluminescent tetrode of the present application is not limited to the materials listed below in the present application,

specifically, the same or different light-emitting materials can be selected for each sub-light-emitting layer, and each sub-light-emitting layer can be independently selected from the group consisting of a polymer organic light-emitting material, a small molecule organic fluorescent material, a small molecule phosphorescent light-emitting material, and a TADF thermal retardation light-emitting material.

Polymeric organic light emitting materials include, but are not limited to, Super yellow, poly [ {2, 5-bis (3',7' -dimethyloctyloxy) -1, 4-phenylacetylene } -co- {3- (4'- (3 ", 7" -dimethyloctyloxy) phenyl) -1, 4-phenylacetylene } -co- {3- (3' - (3 ", 7" -dimethyloctyloxy) phenyl) -1, 4-phenylacetylene } ]), Bu-PPP (poly (2, 5-dibutoxybenzene-1, 4-diyl)), PFO (poly (9, 9-di-n-octylfluorenyl-2, 7-diyl)), PVK (poly (9-vinylcarbazole)), F8BT (poly [ (9, 9-dioctylfluorenyl-2, 7-diyl) -alt- (benzo [2,1,3] thiadiazole-4, 8-diyl) ]), MEH-PPV (poly [ 2-methoxy-5- (2-ethylhexyloxy) -1, 4-phenylacetylene ]), PFO (DMP end capped) (poly (9, 9-di-N-octylfluorenyl-2, 7-diyl), m-xylene capped), PFOPV (poly [ (9, 9-di-N-octylfluorenyl-2, 7-phenylenethylene) -alt- (2-methoxy-5- (2-ethylhexyloxy) -1, 4-diyl) ]), TFB (poly [ (9, 9-di-N-octylfluorenyl-2, 7-diyl) -alt- (4,4' - (N- (4-N-butyl) phenyl) -diphenylamine) ]) Pfoba (poly (9, 9-dioctylfluorene-2, 7-diyl) -alt- (N, N '-diphenylbenzidine-N, N' -diyl)), PFB (poly [ (N, N '- (4-N-butylphenyl) -N, N' -diphenyl-1, 4-phenylenediamine) -alt- (9, 9-di-N-octylfluorenyl-2, 7-diyl) ]), MDMO-PPV (poly [ 2-methoxy-5- [ (3, 7-dimethyloctyloxy) -1, 4-benzene ] -1, 2-ethenediyl ]), PCz (poly [9- (1-octylnonyl) -9H-carbazole ]).

More preferred small molecule organic fluorescent or phosphorescent light emitting materials include, but are not limited to, CBP (4, 4-bis (9-carbazole) biphenyl), Alq3 (tris (8-hydroxyquinoline) aluminum), TBCPF (9, 9-bis-4, 4' - (3, 6-di-tert-butylcarbazolyl) -phenylfluorene), mCP (1, 3-bis-9-carbazolylbenzene), 26DCzPPY (2, 6-bis ((9H-carbazol-9-yl) -3, 1-phenylene) pyridine), ir (mppy)3, ir (piq)2(acac), ir (hpiq)3, ir (ppy)3, ir (bt)2(acac), ir (pbi)2(acac), ir (ppy)2(acac), FCNIrPic, PhFIrPic, PO-01-TB (acetyl acetonate bis (4- (4-tert-butyl-phenyl) -thiophene [ 3], 2-C ] pyridine-C2, N) iridium (III)), PO-01 (bis (4-phenyl-thiophene [3,2-C ] pyridine-C2, N) iridium (III)) acetylacetonate, 6, 12-dobenzylchrylene AND one or more of the alpha, beta-AND series.

A Thermally Activated Delayed Fluorescence (TADF) material is a third generation organic light emitting material that has been developed following organic fluorescent materials and organic phosphorescent materials. Such materials typically have a small singlet-triplet energy level Difference (DEST), and triplet excitons may be converted to singlet excitons for emission by intersystem crossing. This can make full use of singlet excitons and triplet excitons formed under electrical excitation, and the internal quantum efficiency of the device can reach 100%. Meanwhile, the material has controllable structure, stable property, low price and no need of precious metal, and has wide application prospect in the field of OLEDs. More preferably, TADF thermal delay phosphors include, but are not limited to, BCPO (bis-4 (N-carbazolylphenyl) phenylphosphine oxide), 2CzPN (4, 5-bis (9-carbazolyl) -phthalodinitrile), 4CzPN (3,4,5, 6-tetrakis (9-carbazolyl) -phthalodinitrile), 4CzIPN (2,4,5, 6-tetrakis (9-carbazolyl) -isophthalonitrile), 4CzTPN (2,3,5, 6-tetrakis (9-carbazolyl) -terephthalonitrile), 4CzTPN-Bu (2,3,5, 6-tetrakis (3, 6-di-tert-butyl-9-carbazolyl) -terephthalonitrile), 4CzPN-Ph (3,4,5, 6-tetrakis (3, 6-diphenyl-9-carbazolyl) -terephthalonitrile), 4CzTPN-Ph (2,3,5, 6-tetra (3, 6-diphenyl-9-carbazolyl) -terephthalonitrile), 4CzPN-Bu (3,4,5, 6-tetra (3, 6-di-tert-butyl-9-carbazolyl) -terephthalonitrile), DMAC-DPS (bis [4- (9, 9-dimethyl-9, 10-dihydroacridine) phenyl ] sulfolane), DPEPO (bis [2- ((oxo) diphenylphosphino) phenyl ] ether), 2, 6-bis [ 4-dianilinophenyl ] -9, 10-anthraquinone or a plurality of compounds thereof.

TADF luminescent material references are found in:

Scientific Reports,2015,5,8429；

Advanced Functional Materials,2014,24,6178-6186；

Nature Photonics,2014,8,326-332；

Advanced Materials,2014,26,5198-5204。

inorganic luminescent materials or organic-inorganic hybrid luminescent materials known to those skilled in the art to have similar luminescent principles to organic electroluminescent materials may also be within the scope of the luminescent material selection. Such as perovskite luminescent materials, quantum dot luminescent materials, inorganic semiconductor LED materials, and the like.

The perovskite material can be absorbed in the spectral range of 390-790 nm, and has the characteristics of ultra-large light absorption coefficient, ultra-low volume defect density, slow Auger recombination, balanced bipolar transmission and the like, so that the perovskite material has remarkable advantages in the aspect of high luminous efficiency. Meanwhile, due to the characteristics of solution-soluble processing, flexible device preparation and the like of the perovskite material, the preparation of a large-area device with simple process and low price becomes possible, and the perovskite material has wide application prospects in the aspects of display, illumination and optical communication. More preferably, the inorganic or organic-inorganic hybrid perovskite luminescent material is CsPbX₃,CH₃NH₃PbX₃Two-dimensional perovskites such as (PMA)₂PbX₄Or (NMA)₂PbX₄One or more of (wherein, X ═ Cl, Br or I, PMA is benzylamine group, NMA is naphthylmethylamine group).

Perovskite luminescent material references are found in:

Advanced Functional Materials,2016,26,4797-4802；

Nature Photonics,2016,10,699-704；

Science,2015,350,1222-1225；

Advanced materials,2015,27,2311-2316；

Angewandte Chemie International Edition,2016,55,8328-8。

quantum dot materials, which may also be referred to as nanocrystals, are nanoparticles composed of group II-VI or III-V elements. The particle size of the quantum dot is generally between 1-10 nm, and because electrons and holes are limited by quanta, a continuous energy band structure is changed into a discrete energy level structure with molecular characteristics, and the quantum dot can emit fluorescence after being excited. More preferably, the quantum dot material comprises 3D or 2D perovskite quantum dots, carbon quantum dots, and ZnS, ZnSe, ZnO, ZnTe, CdSe, CdS, CdTe, CaS, SrS based on the above perovskite materials. The quantum dots may be single-component, multi-component, core-shell structures, and the like. Meanwhile, the shapes of the nano-particles can be nano-particles, nano-ribbons, nano-wires and the like.

The related references of quantum dot luminescent materials are found in:

Nature Photonics,2008,2,247-250；

Nano letters,2009,9,2532-2536；

Nature photonics,2013,7,407-412；

Organic Electronics,2003,4,123-130；

Advanced Materials,2010,22,3076-3080。

the inorganic semiconductor LED light emitting material is made of a compound containing gallium (Ga), arsenic (As), phosphorus (P), nitrogen (N), or the like. The light emitting principle is the same as that of OLED, and when the electrons and the holes are combined, the light emitting diode can radiate visible light, so that the light emitting diode can be made into an electroluminescent tetrode which integrates the functions of light emitting, switching and color control. Preferably, the inorganic semiconductor LED luminescent material may be made of one or more of the following doped or undoped materials: aluminum gallium arsenide, gallium arsenide phosphide, indium gallium phosphide, aluminum gallium phosphide (doped zinc oxide), aluminum gallium phosphide, indium gallium nitride/gallium nitride, gallium phosphide, indium gallium aluminum phosphide, aluminum gallium phosphide, aluminum indium phosphide, gallium arsenide phosphide, indium gallium aluminum phosphide, gallium arsenide phosphide, gallium phosphide, gallium arsenide phosphide, gallium selenide, indium gallium nitride, silicon carbide, gallium nitride, indium gallium nitride, zinc selenide, sapphire, silicon carbide, diamond, aluminum nitride, aluminum gallium nitride, and the like. Preferably, the size of the device made of the inorganic semiconductor LED luminescent material as the luminescent layer material can be in the nanometer scale, the micrometer scale or the millimeter scale. More preferably, the light-emitting layer is composed of a PN junction formed by doping one or more of the above inorganic semiconductor LED light-emitting materials.

It should be noted that. The luminescent layer of the invention can be further doped with materials such as carbon nano-tubes, nano-silver wires, metal oxides and the like to improve the luminescent property.

The material of each electrode is selected from any type of conductive material, including but not limited to various metals, such as silver, aluminum, gold, copper, platinum, nickel, palladium, iron, magnesium aluminum alloy, copper silver alloy, aluminum copper alloy, iron copper silver alloy, and the like, or metal carbon/nitride (MXene), graphene, graphite, carbon black, carbon fiber, single-walled carbon nanotube, multi-walled carbon nanotube with a two-dimensional layered structure, or one or more of conductive polymer material, conductive elastomer, and conductive oxide containing PEDOT, PANi, Ppy, and the like.

In a preferred implementation of the embodiment of the present invention, as shown in fig. 1 to 10, the modulation layer 2 is an electron conductor layer or an ion conductor layer.

The modulation layer may be made of any electronic conductor or ionic conductor material, including various metals, such as silver, aluminum, gold, copper, platinum, nickel, palladium, iron, magnesium aluminum alloy, copper silver alloy, aluminum copper alloy, iron copper silver alloy, etc., or metal carbon/nitride (MXene), graphene, graphite, carbon black, carbon fiber, single-walled carbon nanotube, multi-walled carbon nanotube with two-dimensional layered structure, or one or more of conductive polymer material, conductive elastomer, conductive oxide containing PEDOT, PANi, Ppy, etc.

In one embodiment, the electrodes are disposed in the same plane of the device structure and separated from each other, are respectively connected to three output terminals of the driving voltage, and correspond to the sub-light emitting layers in vertical space.

In a preferred implementation manner of the embodiment of the present invention, as shown in fig. 1 to 10, the electroluminescent tetrode further includes:

a first direct current blocking layer located between the electrode layer and the light emitting layer; and/or

And the second direct current blocking layer is positioned between the light emitting layer and the modulation layer.

Specifically, the dc blocking layer 3 is a layer that blocks the passage of dc current, and in the electroluminescent tetrode, there may be no dc blocking layer (as shown in fig. 10), only one dc blocking layer 3 (as shown in fig. 1 to 8), two dc blocking layers 3 (as shown in fig. 9), or a plurality of dc blocking layers. The direct current can be blocked by arranging one direct current blocking layer, and the direct current can be more fully blocked by arranging two or more direct current blocking layers.

In a preferred implementation manner of the embodiment of the present invention, the first direct current blocking layer is a dielectric layer; the second direct current barrier layer adopts a dielectric layer.

Specifically, the DC blocking layer is made of dielectric material with high dielectric constant, such as ceramic-like alumina, corundum, barium titanate, mullite, forsterite, magnesia, zirconia, zircon, boron nitride, aluminum nitride, beryllium oxide, spodumene, various glass ceramics, etc., or polyvinylidene fluoride, polytetrafluoroethylene, polyvinylidene fluoride-trifluoroethylene copolymer (P (VDF-TrFE), P (VDF-TrFE-CTFE), P (VDF-TrFE-CFE), polystyrene, polyvinyl alcohol, polyvinylpyrrolidone, polymethyl methacrylate, tetrafluoroethylene hexafluoropropyl copolymer, poly-4-methyl-1-pentene, polypropylene, polyethylene, polychlorotrifluoroethylene, polyphenylene ether, polycarbonate, ethylcellulose, CYTOP, polyethylene terephthalate, parylene (P-xylene polymer), and the like, which are polymer plastics.

In a preferred implementation manner of the embodiment of the present invention, as shown in fig. 1 to 10, the electroluminescent tetrode further includes:

and a hole generation layer 4 connected to the light-emitting layer 5.

Specifically, the hole generation layer is a layer capable of generating holes, and the holes are generated through the hole generation layer, so that the concentration of the holes is increased, and more holes and electrons can be recombined on the light emitting layer to emit light, and the light emitting efficiency is improved. One side of the hole generation layer is connected to the light-emitting layer, the other side of the hole generation layer is connected to the electrode layer (or the modulation layer), and a dc blocking layer may be provided between the hole generation layer and the electrode layer or between the hole generation layer and the modulation layer. Of course, the dc blocking layer may also be provided between the hole generating layer and the light emitting layer.

In a preferred implementation manner of the embodiment of the present invention, the hole generation layer is a stacked layer or a doped structure.

Specifically, a carrier generation layer may be generally employed as the hole generation layer, for example, a structure and a material of a carrier generation layer widely used in a stacked OLED device, generally a stacked layer or a doped structure. The following types are generally classified: n-type doped organic/inorganic metal oxide, N-type doped organic/organic, N-type doped organic/P-type doped organic, N-type organic/P-type organic.

For references relating to hole-generating layers see:

Advanced Functional Materials，2012，22(4)：855-860；

Advanced Materials，2006，18(3)：339—342；

Nanoscale,2020,12(32):17020-17028；

AIP Advances,2020,10(7):075316；

Organic Electronics,2020,83:105745；

Advanced Materials,2015,24(40):5408-5427。

in a preferred implementation manner of the embodiment of the present invention, as shown in fig. 1 to 10, the electroluminescent tetrode further includes:

an electron transport layer 6 connected to the light-emitting layer 5;

an electron injection layer 7 connected to the electron transport layer 6;

the electron transport layer and the hole generation layer are respectively positioned on two sides of the light emitting layer.

Specifically, in order to improve the electron transport efficiency and the electron injection efficiency, an electron transport layer and an electron injection layer may be provided. Of course, only the electron transport layer or the electron injection layer may be provided, or both the electron transport layer and the electron injection layer may be provided (as shown in FIGS. 1 to 10). The electron transport layer and the electron injection layer are located between the electrode layer (or the modulation layer) and the light emitting layer, and when the electron transport layer and the electron injection layer are simultaneously provided, the electron transport layer is located on a side close to the light emitting layer, and the electron injection layer is located on a side close to the electrode layer (or the modulation layer), for example, the electron transport layer is connected to the light emitting layer, and the electron injection layer is connected to the electron transport layer. A dc blocking layer may be disposed between the electron injection layer and the electrode layer. Of course, the dc blocking layer may also be disposed between the light-emitting layer and the electron transport layer, or between the electron transport layer and the electron injection layer.

The material of the electron transport layer may be 1,3, 5-tris (2-N-benzene-benzimidazole) benzene (TPBi), 1,3, 5-tris [ (3-pyridyl) -3-phenyl ] benzene (TmPyPB), 1, 3-bis (3, 5-bipyridin-3-ylphenyl) benzene (BmPyPhB), 4, 7-diphenyl-1, 10-phenanthroline (Bphen), or the like, but is not limited thereto.

The material of the electron injection layer can be LiF and Cs₂CO₃Or (8-hydroxyquinoline) lithium (Liq), and the like are not limited thereto.

In a preferred implementation manner of the embodiment of the present invention, as shown in fig. 1 to 10, the electroluminescent tetrode further includes:

and a substrate 1 connected to the modulation layer 2 or the electrode layer 8.

In particular, in the preparation of electroluminescent tetrodes, the functional layers are usually prepared on the basis of a substrate, which may be removed or left as it is. When the electroluminescent tetrode is prepared, a modulation layer can be prepared on the substrate, or an electrode layer can be prepared on the substrate, so that the substrate is connected with the modulation layer, or the substrate is connected with the electrode layer.

The substrate may be any non-conductive solid material capable of supporting, including plastic, cloth, stone, cement board, ceramic, glass, leather, polymer resin board, wood, or metal plate where metal material is protected by an insulator such as plastic, glass or ceramic, etc. The shape of the base is not limited, and the base can be any shape and size of base material.

Preferably, the substrate is selected from, but not limited to, at least one of glass, quartz, sapphire, or an organic material having flexibility (e.g., PET).

In a preferred implementation manner of the embodiment of the invention, the light emitting colors of the sub-light emitting layers are different.

Specifically, in order to make the electroluminescent tetrode emit light of different colors, and the colors of the light emitted by the sub-light-emitting layers are different, it should be noted that at least two sub-light-emitting layers may emit light of the same color.

In a preferred implementation of the embodiment of the present invention, as shown in fig. 1 and 13, each sub-light emitting layer is spiral-shaped, and each electrode is spiral-shaped.

The shape of each sub-light emitting layer may be set as needed, for example, a square, a circle, a rhombus, or the like, and each sub-light emitting layer is provided in a spiral shape, specifically, a planar spiral shape, in order to improve the light emission uniformity of the light emitting layer. For example, as shown in fig. 11, the electrode layer is circular, the electrode layer is divided into a plurality of parts by using line segments from the center of the electrode layer, that is, one end of each line segment is located at the center of the circle, and then the other end of each line segment is connected to a spiral line, and one electrode is located between two adjacent spiral lines. As shown in fig. 13, the light-emitting layer is circular, and the light-emitting layer is divided into a plurality of portions by using line segments from the center of the light-emitting layer, that is, one end of each line segment is located at the center of the circle, and then the other end of each line segment is connected to a spiral line, and a sub-light-emitting layer is located between two adjacent spiral lines.

Fig. 1 shows the structure of an organic electroluminescent tetrode (OLETe) in one embodiment designed according to this disclosure. In this embodiment, the device structure includes, from top to bottom, a substrate 1, a modulation layer 2, a direct current blocking layer 3, a hole generation layer 4, a light emitting layer 5, an electron transport layer 6, an electron injection layer 7, and an electrode layer 8. The electrode layer 8 comprises three coplanar electrodes (8-1, 8-2, 8-3) which are arranged at intervals, and the electrodes are not in contact with each other. The light-emitting layer comprises three sub-light-emitting layers (5-1, 5-2, 5-3) which are in one-to-one correspondence with the electrode layers in a vertical space, and each light-emitting layer respectively uses red, green and blue organic light-emitting materials. The uppermost layer can be additionally provided with a packaging layer for isolating the influence of the external environment, or the uppermost layer can be not additionally provided with the packaging layer. The dc blocking layer 3 may also be disposed on the surface of the electron injection layer 7, such that the electrode 8-1, the electrode 8-2 and the electrode 8-3 are disposed on the surface of the dc blocking layer 3 in a spaced arrangement, as shown in fig. 2. The positions of the modulation layer 2 and the electrode layer 8 can be interchanged, so that the dc blocking layer 3 is disposed on the surface of the electrode layer 8 and the uncovered surface of the electrode layer 8 on the substrate 1, and the modulation layer 2 is disposed on the surface of the electron injection layer 7, as shown in fig. 3. When the dc blocking layer 3 is disposed on the surface of the electron injection layer 7 and the positions of the modulation layer 2 and the electrode layer 8 are interchanged, the device structure is as shown in fig. 4.

The entire device may also adopt an inverted structure in which the electron transport layer and the electron injection layer are disposed below the light emitting layer and the hole generation layer is disposed above the light emitting layer, as shown in fig. 5. On the basis of the device structure, the dc blocking layer 3 may also be disposed on the surface of the hole generating layer 4, such that electrodes, electrodes and electrodes are disposed on the surface of the dc blocking layer 3 in a spaced arrangement, as shown in fig. 6. The positions of the modulation layer 2 and the electrode layer 8 can be interchanged, so that the dc blocking layer 3 is disposed on the surface of the electrode layer 8 and the uncovered surface of the electrode layer 8 on the substrate 1, and the modulation layer 2 is disposed on the surface of the hole generation layer 4, as shown in fig. 7. When the dc blocking layer 3 is disposed on the surface of the hole generating layer 4 and the positions of the modulation layer 2 and the electrode layer 8 are interchanged, the device structure is as shown in fig. 8.

According to the control requirement of the device, the dc blocking layer may also be disposed on the surface of the modulation layer and the surface of the electron injection layer at the same time, as shown in fig. 9. Alternatively, the dc blocking layer may not be applied, as shown in fig. 10.

Based on the electroluminescent tetrode with integrated light emission, switch and color control in any embodiment, the invention also provides a better embodiment of the preparation method of the electroluminescent tetrode with integrated light emission, switch and color control, which comprises the following steps:

the preparation method comprises the following steps:

providing a substrate;

and sequentially preparing an electrode layer, a light-emitting layer and a modulation layer on the substrate, or sequentially preparing the modulation layer, the light-emitting layer and the electrode layer on the substrate to obtain the electroluminescent tetrode.

Of course, after the electrode layer, the light emitting layer and the modulation layer are sequentially prepared on the substrate, or the modulation layer, the light emitting layer and the electrode layer are sequentially prepared on the substrate, the preparation method may further include the steps of:

and removing the substrate.

The resulting electroluminescent tetrode contains no substrate, and if the substrate is not removed, the resulting electroluminescent tetrode contains a substrate.

The modulation layer, the light-emitting layer and the electrode layer can be formed by deposition. Of course, the electroluminescent tetrode may also include other functional layers, such as a dc blocking layer, a hole generation layer, an electron transport layer, or an electron injection layer, and the preparation order of the functional layers may be set or not set according to requirements.

Based on the integrated light emitting, switching and color control electroluminescent tetrode of any of the above embodiments, the present invention further provides a preferred embodiment of a control method of the integrated light emitting, switching and color control electroluminescent tetrode:

the control method of the invention comprises the following steps:

applying a multiphase alternating current to each electrode respectively, and applying a control signal to the modulation layer so as to control the sub-luminescent layers corresponding to the electrodes to emit light respectively; wherein the number of phases of the multi-phase alternating current is the same as the number of the electrodes.

By applying a multiphase alternating current to each electrode and applying a control signal to the modulation layer, the sub-light emitting layer is caused to emit light through the electrodes and the modulation layer.

The control signal includes: a high level and a low level, the voltage of the high level may be greater than the peak voltage of the multi-phase alternating current.

The control signal includes a high level voltage greater than a peak voltage of the multi-phase alternating current and a low level voltage, which may be 0V.

Example 1

In this embodiment, the sub-light emitting layer 5-1 is made of a red light emitting material, the sub-light emitting layer 5-2 is made of a green light emitting material, the sub-light emitting layer 5-3 is made of a blue light emitting material, the red, green, and blue three-color adjustable electroluminescent transistors are prepared by a vacuum thermal evaporation method, and the three light emitting units are arranged in an interdigital electrode shape. The shape of the three-phase interdigital electrode is shown in fig. 11. The chemical structural formulae and corresponding abbreviations of the organic materials used in this example are shown in FIGS. 12A-12J, where FIG. 12A is HATCN (2,3,6,7,10, 11-hexacyano-1, 4,5,8,9, 12-hexaazatriphenylene), FIG. 12B is HTM (1- [4- (10- [1,1' -biphenyl ] -4-yl-9-anthryl) phenyl ] -2-ethyl-1H-benzimidazole), FIG. 2C is H1(5- [3- (4, 6-diphenyl-1, 3, 5-triazin-2-yl) phenyl ] -5, 7-dihydro-7, 7-dimethylindeno [2,1-B ] carbazole), FIG. 12D is H2(5, 7-dihydro-7, 7-dimethyl-5-phenyl-2- (9-phenyl-9H-carbazol-3-yl) indeno [2,1-b ] carbazole), FIG. 12E is H3(9- (1-naphthyl) -10- [4- (2-naphthyl) phenyl ] anthracene), FIG. 12F is RD (bis [2, 4-dimethyl-6- [5- (2-methylpropyl) -2-quinolyl-kN ] phenyl-kC ] (2, 4-pentanedione-kO 2, kO 4) iridium), FIG. 12G is GD (bis [2- (2-pyridyl-N) phenyl-C ] (2, 4-pentanedione-O2, O4) iridium (III)), FIG. 12H is BD (N, N' -bis (2-methylphenyl) -N, n '-bis (6-tert-butyldibenzofuran-4-yl) pyrene-3, 8-diamine), FIG. 12I is ETM (1- [4- [10- (1,1' -biphenyl-4-yl) anthracen-9-yl ] phenyl ] -2-ethyl-1H-benzimidazole), FIG. 12J is Liq (8-hydroxyquinoline lithium). The specific device structure and the thickness of each layer expressed by the organic material abbreviation are as follows:

glass/ITO (120nm)/PVDF (700nm)/HATCN (10nm)/HTM (30nm)/EML-R/G/B (50nm)/ETM (30nm)/Liq (2.5 nm)/aluminum (100 nm); the device structure is shown in fig. 11.

Wherein, EML-R is a luminescent layer of a red luminescent unit and consists of 65% H1: 32.5% H2: 2.5% RD;

EML-G is a light-emitting layer of a green light-emitting unit and consists of 48.8% H1, 48.8% H2, 2.4% GD;

EML-B is the light-emitting layer of the blue light-emitting unit, consisting of 90% H3: 10% BD (50 nm).

Wherein, the ITO conductive film is a modulation layer material; the PVDF material is a direct current barrier layer and plays a role in blocking direct current; HATCN (10nm)/HTM (30nm) together constitute a hole-generating layer; EML-R/G/B is a light-emitting layer; ETM is an electron transport layer material; liq is an electron injection layer material; aluminum is the electrode layer material.

Applying peak value V to three separated electrodes on electrode layer of prepared device_DWhen the three phase differences of the three-phase alternating current are mutually 120 degrees of driving voltage, the light-emitting unit respectively emits red, green and blue light, and the three colors are macroscopically seen to be mixed to display white due to the small inter-digital electrode distance. Digital signals are applied over the adjustment electrode layer for color adjustment. The specific adjustment logic is as follows:

dividing one period of three-phase electricity into 6 equal time segments, respectively coding the 6 time segments into a high level and a low level, recording the high level as 1, and setting a voltage value as V_CThe low level is noted as 0, and the voltage value is 0V. Wherein V_C>V_D. Fig. 14 (a) - (h) show several representative codes, and the code content is cycled with cycles of the driving voltage period. For each light emitting unit of the three-phase electrically driven OLED, although light emission is not generated in the reverse period of the alternating current, the reverse voltage is indispensable for light emission. Therefore, when the control signal encodes the bit 111111, for the three light-emitting units, the potential of the modulation layer is always higher than that of the electrode layer, the directions of the electric fields at the two sides of the light-emitting layer in the three light-emitting units are not changed, which is equivalent to applying a direct current voltage, and the direct current cannot pass through the direct current barrier layer, so that the red, green and blue light-emitting units do not emit light. When the control code is 101111, that is, the second time segment of each driving voltage cycle is at a low level, and the rest time segments are at a high level, only for the red light-emitting unit, the electric fields at the two sides of the light-emitting layer are changed in the second time segment, and the alternating electric field can generate an alternating current signal through the direct current blocking layer to drive the red light-emitting unit to emit light; and even if the control signal voltage of the blue and green light-emitting units is 0V in the second time period, the modulation layer potential is still higher than the electrode layer potential because the driving voltage of the blue and green light-emitting units is less than 0V, and the potential difference value is always greater than 0 and is always in the same direction. Therefore, only the red light emitting cell is normally operated, and the blue and green light emitting cells are not operated. Similarly, only the green light-emitting unit emits light when the control code is 111011, and the control code is 111110Only the blue light emitting unit emits light. The six-digit numbers are coded, and the light-emitting states controlled by each code are different, so that the total number of the codes is 2⁶I.e. 64 light emitting states. The collected CIE coordinates for all lighting states are summarized as shown in fig. 15. The black dots represent the CIE coordinate points of the states, and the visible colors cover a large area of the CIE coordinates, concentrated within the white triangle, and adjustable between blue, green, and red.

Further, the high level amplitude of the control signal is adjusted to control the light emitting brightness of the three light emitting units. The following table shows the variation of brightness of the red, green and blue light emitting units by changing the high level amplitude of different control signals when the codes are 101111, 111011 and 111110 respectively when the effective value of the driving voltage is constant at 53V.

TABLE 1

It is to be understood that the invention is not limited to the examples described above, but that modifications and variations may be effected thereto by those of ordinary skill in the art in light of the foregoing description, and that all such modifications and variations are intended to be within the scope of the invention as defined by the appended claims.