CN210129521U - Stretchable elastic resistive random access memory - Google Patents
Stretchable elastic resistive random access memory Download PDFInfo
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Abstract
The utility model provides a stretchable elastic resistive random access memory, which comprises a functional layer with resistance conversion effect, and a first electrode and a second electrode which are positioned on the upper surface and the lower surface of the functional layer, wherein the functional layer, the first electrode and the second electrode have stretching elasticity, so that the device has good stretching performance; the functional layer is composed of an elastic matrix and electrically insulated magnetic nanoparticles dispersed in the elastic matrix, and when the magnetic nanoparticles form dispersed chain-shaped structural units which are basically arranged in order, the resistance change effect of the device can be kept stable when the device is stretched along the arrangement direction of the chain-shaped structural units. The utility model discloses still provide the preparation method that the catenulate of regulation and control magnetism nanoparticle in elastic matrix distributes through plus magnetic field, have good application prospect in flexible wearable electron device technical field.
Description
Technical Field
The utility model relates to a flexible electronic technology field of can stretching especially relates to a can tensile elasticity random access memory that changes resistance.
Background
The use of stretchable electronics in wearable electronics, electronic skins, and biomedical applications has attracted extensive research interest. The memory as a carrier for data information is considered as an essential element in stretchable electronic devices, and therefore the stretchability of information storage devices is of great importance.
Among many novel nonvolatile memories, a Resistive Random Access Memory (RRAM), also called a memristor, is unique in the next-generation emerging flexible information memory due to advantages of simple structure, easy integration, wide material selection range, high operation speed, low power consumption, long retention time and the like. The memory cell of the resistive random access memory generally comprises an insulating substrate, a first electrode is arranged on the surface of the insulating substrate, an intermediate layer with a Resistance Switching (RS) effect is arranged on the surface of the first electrode, a second electrode is arranged on the surface of the intermediate layer, and when electric pulses are applied between the first electrode and the second electrode, the resistance can be rapidly switched back and forth between a high resistance value and a low resistance value.
At present, some progress has been made in the flexibility of the resistive random access memory, for example, research reports have been made on the stability of the resistive performance of the intermediate layer under the bending condition. However, the stretchable aspect of the resistive random access memory is basically realized based on a structural design, for example, by designing a structure such as a wrinkle, a wave, an island, and the like. In such a structured design, the device is susceptible to cracking under tensile strain due to mismatch of the elastic modulus of the electrode and/or functional layer and the elastic substrate, resulting in failure of the electrical properties of the device. In addition, the structural engineering is complex, the cost is high, the yield is low, the control is difficult, and the device density is low.
SUMMERY OF THE UTILITY MODEL
To the above technical current situation, the utility model discloses aim at realizing the tensile elasticization of resistance type random access memory, especially realize having stable electrical properties under the tensile strain condition.
In order to achieve the above technical object, the present invention provides a stretchable elastic resistance random access memory, including a functional layer having a Resistance Switching (RS) effect, a first electrode being disposed on an upper surface of the functional layer, and a second electrode being disposed on a lower surface of the functional layer; the functional layer has tensile elasticity, the first electrode has tensile elasticity, and the second electrode has tensile elasticity.
In the utility model, the flexibility refers to the performance of deformation such as bending and stretching under the action of external force; the elasticity is a property that it can be deformed such as bending and stretching by an external force and has a certain shape recovery ability when the external force is removed.
The first electrode material is not limited, and comprises one or more of Liquid Metal (LM), metal particle-doped liquid metal, Ag nanowire (AgNWs), Cu nanowire (CuNWs), Carbon Nanotube (CNTs), graphene, metal nanoparticle, conductive polymer and the like.
The second electrode material is not limited, and includes one or more of Liquid Metal (LM), liquid metal doped with metal particles, Ag nanowire (AgNWs), Cu nanowire (CuNWs), Carbon Nanotube (CNTs), graphene, metal nanoparticles, and conductive polymer.
The material of the functional layer is not limited. As one implementation mode, the functional layer is composed of an elastic matrix with tensile properties and magnetic nanoparticles, and the magnetic nanoparticles are dispersed in the elastic matrix to form a material with a Resistance Switching (RS) effect.
The utility model discloses the people find, work as magnetic nano-particle have electrical insulation, and form the chain form constitutional unit of a plurality of dispersions in the elastic matrix material to each chain form constitutional unit arranges neatly, and the upper surface of the directional functional layer of one end of every chain form constitutional unit can obtain stable resistance transition performance when stretching along the direction of arranging of each chain form constitutional unit when the upper surface of the directional functional layer of the other end. The reason for this is probably that, in the process of forming the conductive channel by applying a voltage between the first electrode and the second electrode, the conductive channel is formed along the chain structures due to the existence of the chain structure units, and when the conductive channel is stretched along the arrangement direction of each chain structure unit, since the elastic modulus of the elastic matrix is much lower than that of the magnetic nanoparticles and the size of the chain structure unit is only nanometer, the main deformation occurs in the elastic matrix, and the chain structure is substantially stable, so that the conductive channel is less affected, and the resistance change performance is stable. Namely, when the device is stretched along the arrangement direction of each chain-shaped structure unit, the resistance change effect of the device can be kept stable, so that the problem that the existing stretchable resistance random access memory cannot be normally used due to unstable resistance change effect or failure of a conductive channel in the stretching process is solved.
The elastic base has tensile elasticity, and the elastic base is an insulator. The elastic matrix material is not limited, and comprises one or more of Polydimethylsiloxane (PDMS), Ecoflex, Polyurethane (PU) and the like.
The magnetic nanoparticles are not limited and comprise ferroferric oxide (Fe)3O4)、γ-Fe2O3, etc.
Preferably, the first electrode surface is provided with a first encapsulation layer, and the second electrode surface is provided with a second encapsulation layer. Preferably, the first encapsulation layer has tensile elasticity, and the material thereof is not limited, and includes one or more of Polydimethylsiloxane (PDMS), Ecoflex, Polyurethane (PU), and the like. Preferably, the second encapsulation layer has tensile elasticity, and the material thereof is not limited, and includes one or more of Polydimethylsiloxane (PDMS), Ecoflex, Polyurethane (PU), and the like.
When the functional layer comprises elastic matrix and magnetic nano particle that have tensile properties, magnetic nano particle dispersion when elastic matrix in, the utility model provides a method for preparing tensile resistance type random access memory, this method can arrange along the magnetic force line and form a plurality of chain form constitutional units based on magnetic particle under the effect of external magnetic field to each other electric isolated physical phenomenon between each chain form constitutional unit, apply the magnetic field of certain direction after mixing magnetic particle as packing and the dynamic elastic matrix of flow, make magnetic particle form a plurality of chain form constitutional units of arranging along the magnetic force line direction in the dynamic elastic matrix of flow under the magnetic field effect, and each chain form constitutional unit is electric insulation each other.
That is, the production method includes a step of producing a functional layer, which is produced as follows:
uniformly mixing the magnetic particles with the flowing elastic matrix to obtain a mixture; applying a magnetic field with a certain direction to the mixture, and then curing the mixture.
Preferably, a magnetic field in a vertical direction is applied to the mixture, and more preferably, a uniform magnetic field in a vertical direction is applied to the mixture.
The magnetic field source is not limited, and comprises a magnetic field formed between permanent magnets, a magnetic field generated by an electrified solenoid coil and the like.
The curing method is not limited, and includes catalyst-initiated curing, high-temperature curing, photocuring and the like.
As one implementation mode, the preparation method comprises the following steps:
(1) preparing a first electrode on the surface of the elastic substrate;
(2) preparing a functional layer on the first electrode surface;
(3) and preparing a second electrode on the surface of the functional layer.
In the step (1), preferably, the elastic substrate is subjected to a surface treatment before the first electrode is prepared on the surface of the elastic substrate. The surface treatment method is not limited, and comprises one or more of plasma treatment, ozone surface radiation, surfactant treatment, graft copolymerization treatment and the like.
In the step (1), the preparation method of the first electrode is not limited, and includes depositing the liquid material on the elastic substrate by coating, casting, spraying, printing, inkjet printing and the like, and then curing.
In the step (3), the preparation method of the second electrode is not limited, and includes depositing the liquid material on the elastic substrate by coating, casting, spraying, printing, inkjet printing and the like, and then curing.
As another implementation mode, the preparation method comprises the following steps:
(1) preparing a functional layer on the surface of a soluble substrate;
(2) preparing a first electrode on the surface of the functional layer;
(3) placing the device obtained in the step (2) in a solution to dissolve the substrate and expose the other surface of the functional layer;
(4) and preparing a second electrode on the other surface of the functional layer.
The soluble substrate material is not limited, and comprises one or more of sodium chloride, polyvinyl alcohol, polyvinyl pyrrolidine and the like.
In the step (2), the preparation method of the first electrode is not limited, and includes depositing the liquid material on the elastic substrate by coating, casting, spraying, printing, inkjet printing and the like, and then curing.
In the step (4), the preparation method of the second electrode is not limited, and includes depositing the liquid material on the elastic substrate by coating, casting, spraying, printing, inkjet printing and the like, and then curing.
Compared with the prior art, the utility model discloses following beneficial effect has:
(1) compared with the stretchable resistance random access memory realized by the structural design, the utility model adopts the intrinsic stretchable elastic material, thereby solving the problem that the electrical performance of the device is invalid due to the functional layer cracking caused by the mismatching of the elastic modulus;
(2) as preferred structure, the utility model discloses well functional layer comprises elastic matrix and electrically insulated's magnetism nanoparticle to when magnetism nanoparticle forms a plurality of dispersed, the chain form constitutional unit of neatly arranging basically in this elastic matrix, the resistance change effect of this device can remain stable when stretching the device along the direction of arranging of each chain form constitutional unit, thereby solved current tensile resistance type random access memory because resistance change effect is unstable or the electric conduction is said and is become invalid and unable normal use's a difficult problem in tensile process.
(3) As an optimal preparation method, the utility model discloses mix magnetic nanoparticle and the elastic matrix who flows the attitude, through the distribution of plus magnetic field regulation and control magnetic nanoparticle in elastic matrix, obtain the ordered nanometer micro-structure that is chain form that constitutes by magnetic nanoparticle to obtain the elastic resistance type random access memory that can stretch that can keep reliable and stable electricity performance under the tensile strain condition, have good application prospect in flexible wearable electron device technical field.
Drawings
Fig. 1 is a schematic structural diagram of the stretchable elastic resistive random access memory according to embodiment 1 of the present invention.
Fig. 2 is a flow chart of the stretchable elastic resistance random access memory according to embodiment 1 of the present invention.
Fig. 3 is an optical microscope image of the stretchable elastic resistance random access memory according to embodiment 1 of the present invention.
Fig. 4 is a test chart of the stretchable elastic resistance random access memory according to embodiment 1 of the present invention.
Fig. 5 is a resistance transition characteristic diagram of the stretchable elastic resistance random access memory in embodiment 1 of the present invention under a non-stretched condition.
Fig. 6 is a resistance transition characteristic diagram of the stretchable elastic resistance random access memory according to embodiment 1 of the present invention under a stretched condition.
Detailed Description
The present invention will be described in further detail with reference to the following drawings and examples, which are not intended to limit the invention, but are intended to facilitate the understanding of the invention.
The reference numbers in the figures are: the device comprises an elastic substrate 1, a first electrode 2, a functional layer 3, a second electrode 4, an elastic matrix 5 and magnetic nano-particles 6.
Example 1:
in this embodiment, the stretchable elastic resistive random access memory is composed of an elastic substrate 1, a first electrode 2 located on the surface of the elastic substrate, a functional layer 3 located on the surface of the first electrode and having a Resistance Switching (RS) effect, and a second electrode 4 located on the surface of the functional layer.
The elastic substrate 1 is composed of an elastic material PDMS having tensile properties.
The functional layer is composed of an elastic matrix 5 with tensile property and magnetic nanoparticles 6, in the embodiment, the elastic matrix 5 is PDMS, and the magnetic nanoparticles are Fe3O4Particles, magnetic nanoparticles Fe, as shown in FIG. 13O4The functional layer is dispersed in the elastic matrix PDMS and forms a plurality of dispersed chain structure units, each chain structure unit is vertical, one end of each chain structure unit points to the upper surface of the functional layer, the other end of each chain structure unit points to the upper surface of the functional layer, and each chain structure unit is orderly arranged along the horizontal direction.
The first electrode is made of copper powder doped gallium indium alloy (GIC) having tensile properties and elasticity.
The second electrode is made of copper powder doped gallium indium alloy (GIC) having tensile properties and elasticity.
The preparation method of the stretchable elastic resistive random access memory comprises the following steps:
preparing PDMS: fe3O4The liquid step: dissolving a PDMS precursor and a curing agent in n-hexane according to a mass ratio of 10:1, stirring for 5min to obtain a PDMS solution, and filtering with a 200nm filter. Then adding Fe3O4，Fe3O4The mass of the solution is 1 to 20 weight percent of that of the PDMS solution, stirring and ultrasonic processing are carried out for 30min, and the mass of the PDMS solution is as follows: fe3O4A liquid;
as shown in fig. 2, the resistive random access memory is prepared as follows:
(1) carrying out plasma treatment on the elastic substrate 1 for 5 min;
(2) printing a first electrode 2 with the line width of 100-200 microns on the PDMS processed in the step (1) through a mask to obtain PDMS/GIC;
(3) PDMS was spin coated on PDMS/GIC at 6000 rpm: fe3O4And (2) applying a magnetic field in the vertical direction as shown in figure 1, and finally curing for 2h at 60-80 ℃ to obtain PDMS with an ordered nano microstructure on the PDMS/GIC: fe3O4 Functional layer 3, i.e. resulting in PDMS/GIC/PDMS: fe3O4；
(4) In PDMS/GIC/PDMS: fe3O4Upper mask printing 100-200 linesWide second electrode 4, resulting in stretchable PDMS/GIC/PDMS in a cross array of first and second electrodes: fe3O4A light microscope image of the/GIC device is shown in FIG. 3.
And (3) utilizing a semiconductor parameter measuring instrument to perform the following steps on the prepared PDMS/GIC/PDMS: fe3O4The electrical performance of the/GIC device is tested. As shown in fig. 4, a voltage was applied to the first electrode while keeping the second electrode grounded during testing, and fig. 5 shows the current-voltage (I-V) curve of the device.
The PDMS/GIC/PDMS: fe3O4the/GIC device has good tensile elasticity, for the PDMS/GIC/PDMS: fe3O4The electrical performance of the device under the tensile condition was tested by applying a horizontal tensile force to the/GIC device to make the device to be strained by 5% in the horizontal direction, and then keeping the above test condition unchanged, and the current-voltage (I-V) curve thereof is shown in fig. 6.
As can be seen from fig. 5 and 6, the PDMS/GIC/PDMS: fe3O4When the/GIC device is horizontally stretched, the resistance change effect of the device is kept stable, and the problem that the conventional stretchable resistance random access memory cannot be normally used due to unstable resistance change effect or failure of a conductive channel in the stretching process is solved.
Example 2:
in this embodiment, the stretchable resistive random access memory is composed of a first package layer, a first electrode located on a surface of the first package layer, a functional layer with a Resistance Switching (RS) effect located on a surface of the first electrode, a second electrode located on a surface of the functional layer, and a second package layer located on a surface of the second electrode.
The first encapsulating layer is made of elastic material PDMS with tensile properties.
The second encapsulating layer is made of elastic material PDMS with tensile properties.
The functional layer is composed of an elastic matrix with tensile property and magnetic nanoparticles, in the embodiment, the elastic matrix is PDMS, and the magnetic nanoparticles are Fe3O4Particles, magnetic nanoparticles Fe3O4Dispersed in an elastomeric matrix PDMSAnd a plurality of scattered chain structure units are formed, each chain structure unit is vertical, one end of each chain structure unit points to the upper surface of the functional layer, the other end of each chain structure unit points to the upper surface of the functional layer, and the chain structure units are regularly arranged along the horizontal direction.
The first electrode is made of gallium indium alloy (GIC) having tensile properties and doped with copper powder.
The second electrode is made of gallium indium alloy (GIC) having tensile properties and doped with copper powder.
The preparation method of the stretchable resistance random access memory comprises the following steps:
preparing PDMS: fe3O4The liquid step: dissolving a PDMS precursor and a curing agent in n-hexane according to a mass ratio of 10:1, stirring for 5min to obtain a PDMS solution, and filtering with a 200nm filter. Then adding Fe3O4，Fe3O4The mass of the solution is 20 wt% of that of the PDMS solution, stirring and ultrasonic processing are carried out for 30min, and the mass of PDMS: fe3O4A solution;
the resistive random access memory is prepared according to the following steps:
(1) carrying out plasma treatment on NaCl for 5 min;
(2) PDMS was spin coated on NaCl at 6000 rpm: fe3O4The solution, then applied with a magnetic field in the vertical direction as shown in fig. 1, was finally cured at 80 ℃ for 2h to obtain PDMS with ordered nano-microstructures on PDMS: fe3O4Functional layers, i.e. resulting in PDMS/PDMS: fe3O4；
(3) In NaCl/PDMS: fe3O4Printing a first electrode with a line width of 200-400 microns by using an upper mask, and packaging by using PDMS to obtain NaCl/PDMS: fe3O4/GIC/PDMS；
(4) The device was NaCl/PDMS: fe3O4immersing/GIC/PDMS in deionized water, and completely dissolving the NaCl sacrificial layer within about 5min to separate the device from the NaCl substrate to obtain PDMS: fe3O4/GIC/PDMS。
(5) In a PDMS: fe3O4200-400 mu of mask printing is carried out on the other surface of the functional layer of the/GIC/PDMSm line width of the second electrode, and packaging with PDMS to obtain PDMS/GIC/PDMS: fe3O4/GIC/PDMS。
And (3) utilizing a semiconductor parameter measuring instrument to perform the following steps on the prepared PDMS/GIC/PDMS: fe3O4And testing the electrical performance of the/GIC/PDMS device. The test method was the same as in example 1, and a current-voltage (I-V) curve was obtained.
The PDMS/GIC/PDMS: fe3O4the/GIC/PDMS device has good tensile elasticity, for which PDMS/GIC/PDMS: fe3O4And applying horizontal tension to the/GIC/PDMS device to enable the device to generate 5% strain in the horizontal direction, keeping the test condition unchanged, and testing the electrical performance of the device under the stretching condition to obtain a current-voltage curve under the stretching condition.
By comparison, the PDMS/GIC/PDMS: fe3O4When the/GIC/PDMS device is horizontally stretched, the resistance change effect of the device is kept stable, and the problem that the conventional stretchable resistance random access memory cannot be normally used due to unstable resistance change effect or failure of a conducting channel in the stretching process is solved.
Example 3:
in this embodiment, the stretchable resistive random access memory is composed of a first package layer, a first electrode located on a surface of the first package layer, a functional layer with a Resistance Switching (RS) effect located on a surface of the first electrode, a second electrode located on a surface of the functional layer, and a second package layer located on a surface of the second electrode.
The first encapsulating layer is made of elastic material PDMS with tensile properties.
The second encapsulating layer is made of elastic material PDMS with tensile properties.
The functional layer is composed of an elastic matrix with tensile property and magnetic nanoparticles, in the embodiment, the elastic matrix is PDMS, and the magnetic nanoparticles are gamma-Fe2O3Particles, magnetic nanoparticles gamma-Fe, as shown in FIG. 12O3Dispersed in the elastic matrix PDMS and formed with a plurality of dispersed chain-like structural units, each of which is vertical and has one end pointing toThe other end of the functional layer points to the upper surface of the functional layer, and the chain-shaped structural units are regularly arranged along the horizontal direction.
The first electrode is composed of CNTs electrode with tensile property and elasticity.
The second electrode is composed of CNTs electrode with tensile property and elasticity.
The preparation method of the stretchable resistance random access memory comprises the following steps:
preparing PDMS: gamma-Fe2O3The liquid step: dissolving a PDMS precursor and a curing agent in n-hexane according to a mass ratio of 10:1, stirring for 5min to obtain a PDMS solution, and filtering with a 200nm filter. Then adding gamma-Fe2O3，γ-Fe2O3The mass of the solution is 15 wt% of that of the PDMS solution, stirring and ultrasonic processing are carried out for 30min, and the mass of PDMS: gamma-Fe2O3A solution;
the resistive random access memory is prepared according to the following steps:
(1) carrying out plasma treatment on NaCl for 5 min;
(2) PDMS was spin coated on NaCl at 6000 rpm: gamma-Fe2O3The solution, then applied with a magnetic field in the vertical direction as shown in fig. 1, was finally cured at 70 ℃ for 2h to obtain PDMS with ordered nano-microstructures on PDMS: gamma-Fe2O3Functional layers, i.e. resulting in PDMS/PDMS: gamma-Fe2O3；
(3) In NaCl/PDMS: gamma-Fe2O3Printing a CNTs electrode with a line width of 200-400 mu m by using an upper mask ink jet, and packaging with PDMS to obtain NaCl/PDMS: gamma-Fe2O3/CNTs/PDMS；
(4) The device was NaCl/PDMS: gamma-Fe2O3soaking/CNTs/PDMS in deionized water, completely dissolving the NaCl sacrificial layer within about 5min, separating the device from the NaCl substrate, and obtaining PDMS: gamma-Fe2O3/CNTs/PDMS。
(5) In a PDMS: gamma-Fe2O3Printing a CNTs electrode with the line width of 200-400 mu m on the other surface of the functional layer of the/CNTs/PDMS through mask ink jet, and packaging the CNTs electrode with the PDMS to obtain a PDMS/CNTs/PDMS: gamma-Fe2O3/CNTs/PDMS。
And (3) utilizing a semiconductor parameter measuring instrument to perform measurement on the prepared PDMS/CNTs/PDMS: gamma-Fe2O3And testing the electrical property of the/CNTs/PDMS device. The test method was the same as in example 1, and a current-voltage (I-V) curve was obtained.
The PDMS/CNTs/PDMS: gamma-Fe2O3the/CNTs/PDMS device has good tensile elasticity, horizontal tensile force is applied to the device to enable the device to generate 5% strain in the horizontal direction, then the testing condition is kept unchanged, and the device under the tensile condition is tested for electrical performance to obtain a current-voltage curve under the tensile condition.
By comparison, the PDMS/CNTs/PDMS: gamma-Fe2O3When the/CNTs/PDMS device is horizontally stretched, the resistance change effect of the device is kept stable, and the problem that the conventional stretchable resistance random access memory cannot be normally used due to unstable resistance change effect or failure of a conducting channel in the stretching process is solved.
The above-mentioned embodiment is right the technical scheme and the beneficial effect of the utility model have been explained in detail, it should be understood that above only be the concrete embodiment of the utility model, and not be used for the restriction the utility model discloses, the fan is in any modification and improvement etc. that the principle within range of the utility model was done all should be contained within the protection scope of the utility model.
Claims (5)
1. A stretchable elastic resistive random access memory is characterized in that: the functional layer has resistance conversion effect and tensile elasticity, the first electrode with tensile elasticity is arranged on the upper surface of the functional layer, and the second electrode with tensile elasticity is arranged on the lower surface of the functional layer.
2. The stretchable elastic resistive-switching random access memory according to claim 1, wherein: the functional layer is composed of an elastic matrix with tensile elasticity and magnetic nanoparticles with electric insulation, and the magnetic nanoparticles are dispersed in the elastic matrix.
3. The stretchable elastic resistive-switching random access memory according to claim 2, wherein: the magnetic nano particles form a plurality of chain-shaped structural units with dispersed electric insulating strips in the elastic base material, and all the chain-shaped structural units are arranged in order; one end of each chain structure unit row points to the upper surface of the functional layer, and the other end of each chain structure unit row points to the upper surface of the functional layer.
4. A stretchable elastic resistive random access memory according to claim 1, 2 or 3, characterized by: the first electrode surface is provided with a first packaging layer, and the second electrode surface is provided with a second packaging layer.
5. A stretchable elastic resistive random access memory according to claim 1, 2 or 3, characterized by: the surface of the first electrode is provided with a first packaging layer with tensile elasticity, and the surface of the second electrode is provided with a second packaging layer with tensile elasticity.
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