CN110189967B - Field emission cathode structure with limited flow resistance variable layer and preparation method thereof - Google Patents
Field emission cathode structure with limited flow resistance variable layer and preparation method thereof Download PDFInfo
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- CN110189967B CN110189967B CN201910590994.XA CN201910590994A CN110189967B CN 110189967 B CN110189967 B CN 110189967B CN 201910590994 A CN201910590994 A CN 201910590994A CN 110189967 B CN110189967 B CN 110189967B
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Abstract
A field emission cathode structure with a limited flow resistance variable layer and a preparation method thereof belong to the technical field of field electron emission. According to the field emission array cathode, a composite memristor material doped with metal ions is adopted between each cathode emitter and the substrate in the field emission array cathode to serve as a resistance change layer, so that the resistance change layer below each cathode emitter controls the migration of the metal ions in the resistance change layer through the current change of the resistance change layer, and is in a low-resistance state when the resistance change function is normally emitted; when short circuit or overcurrent emission occurs, the resistance-change layer is switched to a high resistance state, and different cathode emitters do not influence each other, so that the maximum emission current of a single cathode emitter is limited, and the short circuit or overcurrent emission is inhibited. Compared with the existing current limiting structure, the field emission current limiting structure provided by the invention is simpler, the preparation cost is low, and due to the existence of the resistive layer, the stability of field emission cathode emission is effectively improved while the field emission characteristic is not influenced, and the field emission current limiting structure has great significance for improving the performance of the existing field emission cathode.
Description
Technical Field
The invention belongs to the technical field of field electron emission, and particularly relates to a field emission cathode structure with a limited flow resistance variable layer and a preparation method thereof.
Background
The field emission cathode has the advantages of room-temperature work, quick start, low power consumption, high emission current density and the like, and is a research hotspot of cathode electron sources at home and abroad. A Field emission cathode array (FEA), or Spindt cathode, is a core component of a vacuum Field emission microelectronic device. The traditional Spindt cathode field emission cathode structure is a micro-tip electron gun array processed by a micro-nano process, the array units are cathode-grid assemblies, namely each unit consists of a metal pointed cone emitter growing on an emitter and a grid small hole, and an insulating layer is arranged between the grid and the emitter. Applying a small voltage between the gate and the emitter, the electron energy in the emitter material increases and escapes to form a current, so that the sharp cone generates a significant field emission phenomenon. Due to the limitation of the micro-nano processing technology, even if small fluctuation usually exists in the height of an emitter, the curvature radius of a metal pointed cone and the like in the manufactured field emission cathode array under accurate control, the electric field intensity of the tips of different emitters under the same emission current density is very uneven. The emission current provided by different field emission cathode sharp cones in the field emission array cathode is inconsistent, part of the higher and sharper cathode emitters reach the threshold voltage of field emission first and start to emit electrons, and if the rest cathodes also reach the threshold voltage of emission, the applied voltage needs to be increased continuously. The larger the size of the field emission cathode array, the more severe the limitation of the emission current density non-uniformity to the current load. Therefore, the stability of field emission cathode emission is the key to restrict the performance improvement of vacuum field emission microelectronic devices, and the research of a stable field emission cathode with excellent performance is an urgent need of people.
The current mainstream solution is to introduce a current limiting structure between a field emission cathode emitter and a substrate electrode, and the current limiting structure comprises a resistor, a field effect transistor and a PN junction. The current limiting structure of the field emission cathode emitter series resistor utilizes the voltage division function of the resistor to form negative feedback, so that instantaneous heavy current is inhibited, and the effect of stabilizing current is achieved, but the resistance value of the resistor which can achieve the voltage division function is usually up to megaohm, and dynamic adjustment cannot be achieved; the current limiting structure of the field emission cathode emitter in series connection with the field effect transistor utilizes the constant current region characteristic of the field effect transistor or the characteristic that channel resistance changes along with grid voltage to inhibit the fluctuation of field emission current, and has the advantages of complex structure, complex manufacturing process and high cost; the current limiting structure of the field emission cathode emitter connected with the PN junction in series utilizes the current characteristic of the PN junction working at reverse bias voltage to improve the stability and uniformity of the emission current of the field emission cathode array, and the reverse saturation current of the PN junction is usually extremely small, about nA level, so that the requirement of the field emission cathode emission current is difficult to meet. Therefore, it is very important to find a simple and effective structure to improve the uniformity and stability of field emission cathode emission.
Disclosure of Invention
The invention provides a field emission cathode structure with a limited flow variable layer aiming at the problems of the field emission cathode current limiting structure design in the prior art, the preparation is simple, the cost is low, and the simple field emission current limiting structure can solve the problem of device damage caused by cathode-grid short circuit or over-current emission caused by uneven emission current density in a field emission array cathode and improve the stability of the cathode.
In order to solve the technical problems, the invention adopts the following technical scheme:
a field emission cathode structure with a limited flow resistance variable layer comprises a cathode assembly, a grid assembly and an insulating layer, wherein the cathode assembly is arranged on a substrate and is formed by a cathode, a grid and an insulating layer.
Furthermore, the cathode emitter and the resistance change layer are electrically connected, namely a rheostat is connected below the cathode emitter in series.
Further, the cathode-gate assembly specifically comprises a cathode, a gate arranged on the periphery of the cathode, and an insulating layer arranged between the cathode and the gate, wherein the cathode comprises a cathode emitter and a current limiting structure below the cathode emitter.
Further, the memristive material comprises a binary oxide, a perovskite complex oxide and an organic memristive material.
Specifically, the binary oxide includes SiOx、TiOx。
Specifically, the perovskite-type complex oxide includes, for example, SrTiO3、LaMnO3。
Specifically, the organic memristive material comprises Oxidized Polyethylene (OPE) and zinc tetraphenylporphyrin (ZnTPP).
The resistance change layer can directly select the memristor material doped with metal ions, and can also be doped with the metal ions on the basis of the memristor material.
Further, the selection of the metal ion may be Ag ion or Cu ion.
Preferably, the preparation method of the composite material comprises but is not limited to thermal diffusion technology and ion implantation technology.
Further, the material of the gate electrode can be highly conductive material or thin film such as heavily doped silicon, silver and the like, such as an ITO thin film, a nickel thin film.
Further, the structure of the cathode emitter may be a pointed cone shape.
The invention achieves the purpose of limiting current or avoiding cathode-grid short circuit by arranging the resistance-change layer electrically connected with each cathode emitter so as to avoid that part of the cathode emitters are burnt due to violent emission and further influence the work of the whole array. The normal working current of the field emission cathode is a safe current value which can be stably emitted by a single emitter, and the adjustment of the saturation current can be realized by regulating and controlling the grid voltage.
In another aspect, the present invention provides a method for preparing the field emission cathode, comprising the following steps:
the method comprises the steps of manufacturing an insulating layer on a cleaned substrate, manufacturing a metal grid on the insulating layer, manufacturing an array pattern, etching the metal grid and the insulating layer at the position of an array unit to form a cavity structure, sequentially depositing a composite memristor material doped with metal ions and a cathode emitter material in the cavity, and cleaning to obtain the field emission cathode structure with the current-limiting resistance-change layer.
Further, the preparation of the metal ion-doped composite memristor material is specifically as follows: firstly depositing a memristor material in a cavity, then forming a metal layer on the memristor layer, then depositing the memristor layer on the metal layer, diffusing metal into the memristor layer through high-temperature annealing, and uniformly distributing metal ions in the memristor layer, so as to prepare the composite memristor material doped with the metal ions. When the memristive material is doped with metal ions, the metal ions do not need to be doped.
Compared with the prior art, the invention has the beneficial effects that:
in the field emission array cathode, a composite resistance change material doped with metal ions is arranged between each cathode emitter and a substrate to serve as a resistance change layer, namely, a resistance change device is connected in series below each cathode emitter, and the resistance value of the resistance change device is dynamically adjusted by controlling the migration of the metal ions in the resistance change layer through current change: when the cathode emitter emits normally, the resistance change layer is in a low resistance state; when the cathode emitter and the grid electrode are in short circuit or generate over-current emission, the resistance-change layer is switched to a high-resistance state; and different cathode emitters do not influence each other, so that the maximum emission current of a single cathode emitter can be limited, and short circuit or over-current emission can be inhibited. Compared with the existing current limiting structure, the field emission current limiting structure designed by the invention is simpler, has low preparation cost, can realize the effect of effectively improving the emission stability of the field emission cathode without influencing the field emission characteristic, and has great significance for improving the performance of the existing field emission cathode.
Drawings
Fig. 1 is a schematic diagram of a field emission cathode structure with a current-limiting resistive layer according to the present invention, in which fig. 1 is a substrate layer, 2 is a resistive layer, 3 is a cathode emitter, 4 is an insulating layer, and 5 is a gate.
Fig. 2 is a schematic diagram of the distribution of metal ions in the resistive layer during normal operation of the field emission cathode structure provided by the present invention.
Fig. 3 is a schematic diagram of the distribution of metal ions in the resistive layer when the field emission cathode structure provided by the present invention is in short circuit or over-current emission.
FIG. 4 is an I-V characteristic test curve of a resistive layer in a field emission cathode structure according to the present invention.
Detailed Description
So that those skilled in the art can better understand the principle and the scheme of the present invention, the following detailed description is given with reference to the accompanying drawings and specific embodiments. The teachings of the present invention are not limited to any particular embodiment nor represent the best embodiment, and general alternatives known to those skilled in the art are also encompassed within the scope of the present invention.
The invention provides a field emission cathode structure with a limited flow resistance variable layer, which is structurally shown in figure 1 and comprises a cathode-gate assembly arranged on a substrate 1, wherein the cathode-gate assembly specifically comprises a cathode, a gate 5 arranged on the periphery of the cathode and an insulating layer 4 arranged between the cathode and the gate 5, the cathode comprises a cathode emitter 3 and a current limiting structure below the cathode emitter 3.
In the field emission cathode structure, the migration of metal ions in the resistance change layer is controlled by the current change of a single emitter so as to realize the resistance change function: as shown in fig. 2, when the field emission cathode is in a normal operating state, metal ions are uniformly distributed in the resistive layer, and the resistive layer is in a low resistance state; as shown in fig. 3, when short-circuit or overcurrent emission occurs, metal ions migrate to the boundary of the resistive layer under the action of a strong electric field, and the resistive layer switches to a high resistance state, resulting in voltage drop and emission current drop.
Example 1;
the embodiment provides a preparation method of a field emission cathode with a limited flow resistance variable layer, which comprises the following steps:
step A: silicon wafer selection and cleaning
In the embodiment, a P-type lightly doped silicon wafer with a resistivity of about 3-25 Ω/cm is selected-3The crystal orientation is 100, and deionized water, ethanol, acetone, SC-1, SC-2 and deionized water are sequentially used for ultrasonic cleaning;
and B: manufacturing method of Spindt field emission cavity structure
Manufacturing an insulating layer by adopting an oxidation process, manufacturing a metal grid electrode by adopting a sputtering coating process, manufacturing an array pattern based on a photoetching process and manufacturing a cavity structure by adopting an etching process;
and C: preparation of resistance change layer of metal ion doped memristor material
First, a silicon oxide layer (SiO) is deposited in the cavityx) Then, plating a silver film on the silicon oxide layer by adopting a sputtering coating process, depositing a layer of silicon oxide layer after sputtering is finished, and diffusing silver into the silicon oxide layer by high-temperature annealing so as to uniformly distribute silver ions in the silicon oxide layer;
step D: cathode for electron beam evaporation
Evaporating a layer of aluminum as a sacrificial layer, and then evaporating a cathode material by an electron beam evaporation method to form a cone cathode emitter;
step E: sacrificial layer removal
Preparing corrosive liquid, heating in a water bath, putting a sample wafer, putting the sample wafer into an ultrasonic instrument for ultrasonic treatment until the sacrificial layer falls off, cleaning with warm deionized water for several times, and drying for later use.
The present embodiment was tested using Gilbert-Stokes (KEITHLEY) to obtain the I-V characteristic curve of the resistance change layer, as shown in FIG. 4. It can be seen from the figure that the resistance-change layer in the forward region of 0-VON section is low resistance corresponding to the normal working time of the field emission cathode in figure 2, and corresponds to the uniform distribution state of metal ions; the VON-cutoff voltage corresponds to the resistance layer being switched to the high resistance state when the field emission cathode in fig. 3 is short-circuited or over-current emitted, and corresponds to the metal ions in the resistance layer being pushed to one side of the resistance layer, thereby switching the resistance layer to the ion distribution state of the high resistance state.
Example 2:
the embodiment provides a preparation method of a field emission cathode with a limited flow resistance variable layer, which comprises the following steps:
step A: silicon wafer selection and cleaning
In the embodiment, a P-type lightly doped silicon wafer with a resistivity of about 3-25 Ω/cm is selected-3The crystal orientation is 100, and deionized water, ethanol, acetone, SC-1, SC-2 and deionized water are sequentially used for ultrasonic cleaning;
and B: manufacturing method of Spindt field emission cavity structure
Manufacturing an insulating layer by adopting an oxidation process, manufacturing a metal grid electrode by adopting a sputtering coating process, manufacturing an array pattern based on a photoetching process and manufacturing a cavity structure by adopting an etching process;
and C: preparation of resistance change layer of metal ion doped memristor material
First, a titanium oxide layer (TiO) is deposited in the cavityx) Then, plating a silver film on the titanium oxide layer by adopting a sputtering coating process, depositing a titanium oxide layer after sputtering is finished, and diffusing silver into the titanium oxide layer by high-temperature annealing so as to uniformly distribute silver ions in the titanium oxide layer;
step D: cathode for electron beam evaporation
Evaporating a layer of aluminum as a sacrificial layer, and then evaporating a cathode material by an electron beam evaporation method to form a cone cathode emitter;
step E: sacrificial layer removal
Preparing corrosive liquid, heating in a water bath, putting a sample wafer, putting the sample wafer into an ultrasonic instrument for ultrasonic treatment until the sacrificial layer falls off, cleaning with warm deionized water for several times, and drying for later use.
Example 3:
the embodiment provides a preparation method of a field emission cathode with a limited flow resistance variable layer, which comprises the following steps:
step A: silicon wafer selection and cleaning
In the embodiment, a P-type lightly doped silicon wafer with a resistivity of about 3-25 Ω/cm is selected-3The crystal orientation is 100, and deionized water, ethanol, acetone, SC-1, SC-2 and deionized water are sequentially used for ultrasonic cleaning;
and B: manufacturing method of Spindt field emission cavity structure
Manufacturing an insulating layer by adopting an oxidation process, manufacturing a metal grid electrode by adopting a sputtering coating process, manufacturing an array pattern based on a photoetching process and manufacturing a cavity structure by adopting an etching process;
and C: preparation of resistance change layer of metal ion doped memristor material
Firstly, depositing a LaMnO3 Layer (LMO) in a cavity, then plating a copper film on the LaMnO3 layer by adopting a sputtering coating process, depositing a LaMnO3 layer after sputtering is finished, and diffusing copper into the LaMnO3 layer by high-temperature annealing so that copper ions are uniformly distributed on the LaMnO3 layer;
step D: cathode for electron beam evaporation
Evaporating a layer of aluminum as a sacrificial layer, and then evaporating a cathode material by an electron beam evaporation method to form a cone cathode emitter;
step E: sacrificial layer removal
Preparing corrosive liquid, heating in a water bath, putting a sample wafer, putting the sample wafer into an ultrasonic instrument for ultrasonic treatment until the sacrificial layer falls off, cleaning with warm deionized water for several times, and drying for later use.
Example 4:
the embodiment provides a preparation method of a field emission cathode with a limited flow resistance variable layer, which comprises the following steps:
step A: silicon wafer selection and cleaning
In the embodiment, a P-type lightly doped silicon wafer with a resistivity of about 3-25 Ω/cm is selected-3The crystal orientation is 100, and deionized water, ethanol, acetone, SC-1, SC-2 and deionized water are sequentially used for ultrasonic cleaning;
and B: manufacturing method of Spindt field emission cavity structure
Manufacturing an insulating layer by adopting an oxidation process, manufacturing a metal grid electrode by adopting a sputtering coating process, manufacturing an array pattern based on a photoetching process and manufacturing a cavity structure by adopting an etching process;
and C: preparation of resistance-change layer of metal ion doped organic memristor material
Firstly, a layer of zinc tetraphenylporphyrin (ZnTPP) film is sprayed in the air environment in the cavity, and Zn is coated under an external electric field2+The oxygen ions are uniformly distributed in the organic film, and the oxygen ions are coordinated under the action of an external electric field to generate a memebergy effect.
Step D: cathode for electron beam evaporation
Evaporating a layer of aluminum as a sacrificial layer, and then evaporating a cathode material by an electron beam evaporation method to form a cone cathode emitter;
step E: sacrificial layer removal
Preparing corrosive liquid, heating in a water bath, putting a sample wafer, putting the sample wafer into an ultrasonic instrument for ultrasonic treatment until the sacrificial layer falls off, cleaning with warm deionized water for several times, and drying for later use.
While the present invention has been particularly shown and described with reference to the preferred embodiments, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (10)
1. A field emission cathode structure with a limited current variable layer comprises a cathode assembly, a grid and an insulating layer, wherein the cathode assembly is arranged on a substrate and is formed by a cathode, a grid and an insulating layer, the cathode comprises cathode emitters and a current-limiting structure below the cathode emitters, and the field emission cathode structure is characterized in that a resistance variable layer serving as a current-limiting structure is arranged between each cathode emitter and the substrate, and the resistance variable layer is made of metal ion doped memristive materials.
2. The field emission cathode structure with a current-limiting resistive layer according to claim 1, wherein the cathode-gate assembly comprises a cathode, a gate disposed at the periphery of the cathode, and an insulating layer disposed between the cathode and the gate, and the cathode comprises a cathode emitter and a current-limiting structure thereunder.
3. The field emission cathode structure with a current limiting resistive layer of claim 1, wherein the cathode emitter is electrically connected to the resistive layer.
4. The field emission cathode structure with a current limiting resistive layer according to claim 1, wherein the memristive material comprises a binary oxide, a perovskite complex oxide, or an organic memristive material.
5. The field emission cathode structure with a current limiting resistive layer according to claim 4, wherein the organic memristive material comprises polyethylene oxide or zinc tetraphenylporphyrin.
6. The field emission cathode structure with a current limiting resistive layer according to claim 1, wherein the metal ions comprise Ag ions or Cu ions.
7. The field emission cathode structure with a current limiting resistive layer according to claim 1, wherein the resistive layer is prepared by a method comprising a thermal diffusion technique or an ion implantation technique.
8. The structure of claim 1, wherein the gate material comprises heavily doped silicon, silver, nickel or ITO.
9. A preparation method of a field emission cathode with a limited flow resistance variable layer comprises the following steps:
the method comprises the steps of manufacturing an insulating layer on a cleaned substrate, manufacturing a metal grid on the insulating layer, manufacturing an array pattern, etching the metal grid and the insulating layer at the position of an array unit to form a cavity structure, sequentially depositing a composite memristor material doped with metal ions and a cathode emitter material in the cavity, and cleaning to obtain the field emission cathode with the current-limiting resistance-change layer.
10. The preparation method of claim 9, wherein the composite memristive material doped with metal ions is prepared as follows:
firstly depositing a memristor layer in a cavity, then forming a metal layer on the memristor layer, then depositing the memristor layer on the metal layer, diffusing metal into the memristor layer through high-temperature annealing, and uniformly distributing metal ions in the memristor layer, so as to prepare the composite memristor material doped with the metal ions.
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