CN113285019A - Display memory based on phase-change material - Google Patents
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- CN113285019A CN113285019A CN202110407107.8A CN202110407107A CN113285019A CN 113285019 A CN113285019 A CN 113285019A CN 202110407107 A CN202110407107 A CN 202110407107A CN 113285019 A CN113285019 A CN 113285019A
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N70/00—Solid-state devices without a potential-jump barrier or surface barrier, and specially adapted for rectifying, amplifying, oscillating or switching
- H10N70/20—Multistable switching devices, e.g. memristors
- H10N70/231—Multistable switching devices, e.g. memristors based on solid-state phase change, e.g. between amorphous and crystalline phases, Ovshinsky effect
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect
- G02F1/153—Constructional details
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect
- G02F1/153—Constructional details
- G02F1/155—Electrodes
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect
- G02F1/163—Operation of electrochromic cells, e.g. electrodeposition cells; Circuit arrangements therefor
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10B—ELECTRONIC MEMORY DEVICES
- H10B63/00—Resistance change memory devices, e.g. resistive RAM [ReRAM] devices
- H10B63/80—Arrangements comprising multiple bistable or multi-stable switching components of the same type on a plane parallel to the substrate, e.g. cross-point arrays
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N70/00—Solid-state devices without a potential-jump barrier or surface barrier, and specially adapted for rectifying, amplifying, oscillating or switching
- H10N70/801—Constructional details of multistable switching devices
- H10N70/881—Switching materials
- H10N70/883—Oxides or nitrides
- H10N70/8833—Binary metal oxides, e.g. TaOx
Abstract
The invention relates to a phase-change material-based display memory, which consists of display memory elements, an electric control element and a memory element, wherein the display memory elements are arranged periodically; the structure of each display memory element comprises in sequence: the phase change display device comprises a first transparent electrode layer, a phase change storage layer, an ion conduction layer, a phase change display layer and a second transparent electrode layer; the component of the phase change storage layer is VO2。
Description
Technical Field
The invention relates to a phase-change material-based display and storage integrated device and a preparation method thereof, which are mainly used for phase-change storage, intelligent display and the like and belong to the technical field of functional semiconductors.
Background
Phase change memory PCM uses the difference in resistivity of a phase change material between its two states (crystalline and amorphous) to enable the storage of data "0" and "1". Compared with the current mainstream flash memory, the phase change memory is considered to be one of the most promising nonvolatile memories due to the advantages of simple manufacturing process, low power consumption, strong data storage capacity and the like.
The current high-performance system puts higher requirements on the storage density and the area size of the phase change memory, and the gate tube also becomes one of the key factors of the mass storage of the phase change memory due to the problems of leakage current, large required Reset current and the like of a phase change unit. Vanadium dioxide (VO)2) Has a typical semiconductor metal reversible phase transition (SMT), and VO is formed by the first-order phase transition2The transition from the monoclinic phase (P21/c) to the tetragonal rutile phase (P42/mnm) with a marked change in the electrical and optical properties is an ideal candidate for gate tubes.
Fast digital information display devices play an increasingly important role in many applications, such as computers, smart windows, electronic skins, and wearable devices. Liquid crystal displays have been widely used in the past decades because of their good display quality and fast response. However, conventional display technologies have many limitations, including low energy efficiency, lack of flexibility, and high manufacturing costs. Among them, electrochromic displays, having a variety of device structures, are based primarily on optical responses to bistable and reversible structural changes caused by electronic stimuli. WO3Electrochromic displays are being developed for their "memory effect", large area manufacture and long service lifeThe intelligent display is unique.
Due to the above attractive properties, the phase change material VO2With WO3The method is integrated into a device, a multilayer composite device is designed to realize display and storage integration, and is expected to arouse wide research interest.
Patent 1 (chinese publication No. CN106992251A) discloses a VO-based methodxThe phase change memory cell of the gate tube comprises a lower electrode layer and a VOxA gate layer, a phase change functional layer and an upper electrode layer, which adopts VOxThe gating of the phase change functional layer is realized, and the data storage can be realized on the basis of the gating of the phase change functional layer. However, for the phase change memory, VO has to be able to both reduce the leakage current and ensure a larger operation window2The optimal threshold voltage of the gate tube needs to be determined by performing multiple experimental tests in the array. Patent 2 (chinese publication No. CN104730796A) designs a non-volatile display unit with a "sandwich" structure, which is a structure composed of upper and lower conductive electrodes and a middle phase-change display part. The phase-change material depends on the heat accumulation of different electric pulses, has a changeable phase state structure, and reflects different colors corresponding to different refraction performance and absorption performance. However, the display unit is inconvenient to prepare in a large area, and the color rendering implementation mode is complicated and needs to be implemented through different arrangement combinations of multiple layers of phase-change materials.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a display memory with quick display and nonvolatile storage and a preparation method thereof.
In one aspect, the invention provides a phase change material-based display memory, which is composed of periodically arranged display memory elements, an electric control element connected to the display memory elements, and a memory element; the structure of each display memory element comprises in sequence: the phase change display device comprises a first transparent electrode layer, a phase change storage layer, an ion conduction layer, a phase change display layer and a second transparent electrode layer; what is needed isThe component of the phase change storage layer is VO2。
Preferably, when a forward/reverse voltage is applied between the first transparent electrode layer and the second transparent electrode layer through the electric control element, ions in the ion conduction layer can be reversibly embedded into/removed from the phase change layer, the phase change storage layer realizes the mutual conversion between high and low resistance states, and the display memory can not only display but also synchronously store corresponding electric signals output by the phase change storage layer by using the memory storage element; preferably, the forward voltage may be 1 to 3V, and the reverse voltage may be-1 to-3V.
Preferably, the ion conducting layer is composed of one or more of amorphous aluminum silicate, lithium aluminate, lithium tantalate, lithium nickelate and the like; preferably, the amorphous state thin film has a thickness of 100-200 nm and a light transmittance of more than 85% between 380-760 nm.
In the present invention, Al is passed through the ion conductive layer3+The synchronous realization of the display and the storage of each display storage unit in the device is realized. In addition, no matter which direction the applied voltage acts on, a functional layer realizes independent action, and quick display and signal storage are realized.
Preferably, the composition of the phase change memory layer is monoclinic vanadium dioxide (VO)2(M)); preferably, the thickness of the phase change memory layer is 50-100 nm.
Preferably, the color-changing display layer is WO3、MoO3、NbO3、TiO2And the like.
Preferably, the first transparent electrode layer and the second transparent electrode layer are transparent conductive oxides, preferably one of FTO, ITO, AZO, and NTO; the sheet resistance of the first transparent electrode layer and the second transparent electrode layer is 5-50 omega/cm2And the light transmittance between 350 nm and 800nm is more than 75 percent.
In another aspect, the present invention provides a method for manufacturing a phase change material-based display memory, including:
(1) selecting a transparent conductive oxide as a target material, and depositing a first transparent electrode layer on the surface of a substrate by adopting a magnetron sputtering method;
(2) preparing a phase change storage layer on the first transparent electrode layer by adopting a magnetron sputtering method or a slurry blade coating method;
(3) depositing an ion conducting layer on the surface of the phase change storage layer by adopting a magnetron sputtering method;
(4) generating a phase change display layer on the surface of the ion conducting layer by adopting a magnetron sputtering method, an electroplating method or a spin coating method;
(5) depositing a second transparent electrode layer on the surface of the phase change display layer by adopting a magnetron sputtering method to obtain a display storage element;
(6) and assembling the obtained display memory element, the electric control element and the memory element into a display memory module, and arranging the display memory module according to periodicity to obtain the phase change material-based display memory array.
Has the advantages that:
1. the invention selects phase-change material VO2With WO3The display switching and information storage integrated device is prepared and can be integrated into a large-size high-resolution display storage array;
2. the invention is based on the electric control effect, VO, of the multilayer composite membrane module2The resistance value before and after the phase change is obviously changed to realize signal output, and the memory storage element stores a display state corresponding signal and can feed back the display state corresponding signal to the electric control element to restore the original display state.
Compared with the technical scheme of single phase change display and single phase change storage, the display and storage integrated device based on the phase change material provided by the invention realizes the dual-function integration of light display and electric storage by utilizing the quick reversible transformation of electric control phase change. In addition, the non-volatile display memory designed by the invention adopts the bistable phase-change material, can stably display two color states under the control of an external voltage, and outputs corresponding electric signals for storage, and has the advantages of low display maintaining power consumption, stable display state (non-volatile), short switching time, high conversion speed, flexible form and the like.
Drawings
FIG. 1 is a schematic diagram of a display memory element in a phase change material based display memory according to the present invention;
FIG. 2 is a schematic diagram of the operation of a phase change material based display memory module of the present invention;
FIG. 3 is a schematic diagram of a phase change material based display memory module array according to the present invention.
Detailed Description
The present invention is further illustrated by the following examples, which are to be understood as merely illustrative and not restrictive.
According to the invention, the display storage unit is obtained by designing the multilayer composite film module to combine two phase change material systems, two responses of color development and storage are presented to an applied voltage, the middle ion conduction layer is well attached to the two phase change functional layers at two sides, and a rapid ion transportation effect is provided in the response process.
The invention provides a phase-change material-based display memory module array (or a phase-change material-based display memory), wherein under the action of different voltages output by an electric control element, the high-low resistance state of each display memory element corresponds to the color display state, and the memory element correspondingly stores different electric signals. The display memory module array integrated based on the display memory element, the electric control element and the memory element can provide two display memory schemes. It should be noted that each of the display memory elements may be connected to one of the electronic control elements and one of the memory elements. Alternatively, all the display memory elements may be commonly connected to one electric control element and one memory element. Wherein, the electric control element and the memory storage element can be purchased in the market.
Static mode: for each module unit, when the voltage of the electric control element is adjusted to be downward, cations in the ion conduction layer enter the phase change storage layer, the device is converted into a transparent high-resistance state, and the memory storage element stores a corresponding electric signal 1; correspondingly, when the electric control element adjusts the voltage upwards, the positive ions in the ion conduction layer enter the phase change display layer, the device is converted into a blue low-resistance state, and the memory storage element stores a corresponding electric signal '0'. In the static mode, the display memory module array can perform static pattern display and corresponding signal storage.
Dynamic mode: when the electric control element independently applies corresponding voltage to each module, the display memory module array can carry out dynamic erasing and writing of display patterns.
The present invention will be described in detail by way of examples. It is also to be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the invention, and that certain insubstantial modifications and adaptations of the invention by those skilled in the art may be made in light of the above teachings. The specific process parameters and the like of the following examples are also only one example of suitable ranges, i.e., those skilled in the art can select the appropriate ranges through the description herein, and are not limited to the specific values exemplified below.
Example 1
The glass substrate is ultrasonically cleaned in acetone, ethanol and deionized water respectively, is fixed on a substrate tray and is placed into a magnetron sputtering device, and a transparent conductive material is formed by sputtering: the target material is ITO target material, the sputtering power supply adopts radio frequency power supply, and the power density is 3W/cm2Pure argon atmosphere, pressure of 0.3Pa and sputtering time of 60min to obtain ITO conductive film with smooth surface, thickness of 100-200 nm and surface sheet resistance of 5-50 omega/cm2。
Example 2
VO is formed by sputtering on a glass substrate sputtered with a transparent conductive material2Film formation: the target material is selected from vanadium (V) oxide2O3) The sputtering power supply adopts a direct current power supply, and the power density is 2.5W/cm2Pure argon atmosphere, pressure of 1.5Pa, sputtering time of 15min, then vacuum annealing at 450 ℃ for 5min to obtain VO with flat surface2A thin film having a thickness of 50 to 100 nm.
Example 3
At VO2Sputtering of aluminum silicate (Al) onto filmsxSiOy) Ion conductive layer film: the target material is aluminum silicate target material, the sputtering power source adopts radio frequency power source, and the power density is 2.5W/cm2Pure argon gas is used as atmosphere, the pressure is 2.0Pa, and the sputtering time is 45 minutes at room temperature, so that aluminum silicate (Al) with a smooth surface is obtainedxSiOy) A film. The obtained silicic acidAluminum (Al)xSiOy) The thickness of the film is 100-200 nm, and the light transmittance between 380-760 nm is more than 85%.
Example 4
In the presence of aluminum silicate (Al)xSiOy) Formation of tungsten oxide on a solid ion-conducting layer film (WO)3) The film is obtained by a reactive sputtering method and has amorphous porous loose film. The target material is metal tungsten target material, the sputtering power supply adopts direct current power supply, and the power density is 1.5W/cm2The atmosphere is oxygen-argon mixed gas, wherein the volume ratio of oxygen is 6%, the pressure is 1.0Pa, the sputtering time is 30min at room temperature, and the WO with a smooth surface is obtained3The film has a thickness of 200 to 400 nm. Finally, in WO3The film was prepared as a transparent conductive layer in the same manner as in example 1 and will not be described herein. A display memory based on phase change material is thus obtained.
Claims (7)
1. The display memory based on the phase change material is characterized by comprising display memory elements which are periodically arranged, an electric control element connected with the display memory elements and a memory element; the structure of each display memory element comprises in sequence: the phase change display device comprises a first transparent electrode layer, a phase change storage layer, an ion conduction layer, a phase change display layer and a second transparent electrode layer; the component of the phase change storage layer is VO2。
2. The phase-change-material-based display memory according to claim 1, wherein when a forward/reverse voltage is applied between the first transparent electrode layer and the second transparent electrode layer through the electric control element, ions in the ion conducting layer reversely embed/detach from the phase-change layer, the phase-change memory layer realizes mutual conversion between high and low resistance states, and the display memory can not only display and synchronously store corresponding electric signals output by the phase-change memory layer by using the memory storage element; preferably, the forward voltage is 1-3V, and the reverse voltage is-1-3V.
3. The phase change material based display memory of claim 1 or 2, wherein the phase change storage layer is monoclinic phase vanadium dioxide; preferably, the thickness of the phase change memory layer is 50-100 nm.
4. The phase change material based display memory according to claim 1 or 2, wherein the ion conductive layer is composed of one or more of amorphous aluminum silicate, lithium aluminate, lithium tantalate, lithium nickelate; preferably, the amorphous state thin film has a thickness of 100-200 nm and a light transmittance of more than 85% between 380-760 nm.
5. The phase change material based display memory of claim 1 or 2, wherein the phase change display layer is WO3、MoO3、NbO3、TiO2One of the like; preferably, the thickness of the phase change display layer is 200-400 nm.
6. The phase change material based display memory according to any of claims 1-5, wherein the first and second transparent electrode layers are transparent conductive oxides, preferably one of FTO, ITO, AZO, NTO.
7. The phase change material-based display memory according to claim 6, wherein the sheet resistance of the first transparent electrode layer and the second transparent electrode layer is 5 to 50 Ω/cm2And the light transmittance between 380 nm and 760nm is more than 75 percent.
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