CN111725400A - Resistive random access memory device structure based on partial active metal doped thin film and preparation method thereof - Google Patents

Resistive random access memory device structure based on partial active metal doped thin film and preparation method thereof Download PDF

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Publication number
CN111725400A
CN111725400A CN202010588247.5A CN202010588247A CN111725400A CN 111725400 A CN111725400 A CN 111725400A CN 202010588247 A CN202010588247 A CN 202010588247A CN 111725400 A CN111725400 A CN 111725400A
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dielectric layer
active metal
random access
access memory
resistive random
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宋成
孙一鸣
潘峰
乔磊磊
曾飞
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Tsinghua University
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Tsinghua University
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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
    • 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
    • H10N70/011—Manufacture or treatment of multistable switching devices
    • 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
    • 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
    • H10N70/841—Electrodes

Abstract

The invention discloses a resistive random access memory device structure based on a partial active metal doped thin film and a preparation method thereof. The resistive random access memory comprises a substrate, a bottom electrode, an undoped dielectric layer, an active metal doped dielectric layer and a top electrode from bottom to top in sequence. According to the invention, the active metal is added into the dielectric layer by a doping method, the doped oxide film is essentially used as an electrode, the undoped oxide film is used as the dielectric layer, an electron tunneling type conductive filament formed by active metal nanoclusters is favorably formed in the dielectric layer, the working current of the resistive random access memory can be effectively reduced, and the aim of low power consumption is further realized.

Description

Resistive random access memory device structure based on partial active metal doped thin film and preparation method thereof
Technical Field
The invention belongs to the field of information electronic materials, and particularly relates to a resistive random access memory device structure based on a partial active metal doped thin film and a preparation method thereof.
Background
The memory, as a semiconductor device integrating data storage and data processing, has always been a dominant position in the semiconductor market. As an alternative technical route of the next-generation nonvolatile memory, the resistive random access memory having the structure of "electrode-dielectric layer-electrode" has attracted attention due to its advantages of high response speed, high integration density, high energy efficiency, high compatibility with the existing CMOS process, and the like. Meanwhile, compared with other memory systems, the resistive random access memory has very wide material sources, and common inorganic and organic insulators and semiconductors can be almost used as storage media of the resistive random access memory.
From the current research situation, the development direction of the resistive random access memory is still high speed, high density and high energy efficiency. The working current of the resistive random access memory is a core index, and generally, the lower the working current is, the lower the energy consumed by erasing and writing of a single device is. Therefore, how to prepare the low-working-current resistive random access memory through device design is a research hotspot in the national and foreign academic circles and industrial circles.
Disclosure of Invention
Against the existing background, the invention aims to provide a resistive random access memory structure based on a partially active metal doped thin film and a preparation method thereof, so that a resistive random access memory with low working current and reliable performance can be obtained.
The resistive random access memory provided by the invention sequentially comprises a substrate, a bottom electrode, an undoped dielectric layer, an active metal doped dielectric layer and a top electrode from bottom to top.
In the resistive random access memory, the substrate is commercial Pt (120 nm)/Ti (15 nm)/SiO2a/Si substrate.
The bottom electrode and the top electrode are both selected from any one of inert metals; specifically, the metal is selected from any one of Pt, Au and Pd.
The undoped dielectric layer is an oxide film; in the oxide thin film, the oxide is at least one selected from tantalum oxide, hafnium oxide, titanium oxide, aluminum oxide and zinc oxide;
the active metal doped dielectric layer is an active metal doped oxide film; in the active metal doped oxide film, the oxide is selected from at least one of tantalum oxide, hafnium oxide and zinc oxide; the active metal is at least one of Ag, Cu, Al, Ta and Ru;
the doping concentration of the active metal is 5-20%; in particular 15 percent; the doping concentration of the active metal refers to the molar ratio of the active metal to the metal elements in the oxide, for example, 15% refers to the molar ratio of the active metal to the metal elements in the oxide of 15: 100.
The thickness of the substrate is 200-800 μm;
the thickness of the bottom electrode is 5-100 nm; specifically 10 nm;
the thickness of the undoped dielectric layer is 5-30 nm; specifically 20 nm;
the thickness of the active metal doped dielectric layer is 5-30 nm; specifically 20 nm;
the thickness of the top electrode is 5-100 nm; in particular 50 nm.
More specifically, the resistive random access memory is a resistive random access memory a or a resistive random access memory b with the following structure:
the resistive random access memory a has the following structure: Pt/TaOx:Ag/TaOx/Pt；
The resistive random access memory b has the following structure: Pd/ZnO, Al/ZnO/Pd.
The method for preparing the resistive random access memory comprises the following steps:
and after the dot array is manufactured on the substrate, photoetching is carried out, and then the bottom electrode, the undoped dielectric layer, the active metal doped dielectric layer and the top electrode are sequentially deposited to obtain the resistive random access memory.
In the method, the preparation method of the dot array is ultraviolet exposure or electron beam exposure;
the photoetching is a conventional method, and specifically comprises the steps of surface cleaning and drying, priming, photoresist spinning, soft drying, exposure, post-drying, developing and hard drying;
the method for preparing the bottom electrode and the top electrode is direct-current magnetron sputtering;
the specific conditions of the direct current magnetron sputtering are as follows: background vacuum degree of more than 10-4Pa, using a pure metal target (Pt, Au or Pd); the working atmosphere is pure argon atmosphere; the sputtering pressure is 0.35 Pa; the sputtering power is 5-50W; in particular 30W;
the method for preparing the undoped dielectric layer is radio frequency magnetron sputtering or reactive magnetron sputtering;
specifically, the undoped dielectric layer is TaOx(x is 1.96), depositing by adopting a radio frequency magnetron sputtering tantalum oxide ceramic target;
more specifically, the specific conditions of the radio frequency magnetron sputtering are as follows: background vacuum degree greater than 10-4Pa, using oxide ceramic target Ta2O5(ii) a The working atmosphere is pure argon atmosphere; the sputtering pressure is 0.35 Pa; the sputtering power is 50-200W; in particular 90W;
when the undoped dielectric layer is ZnO, depositing by using a metal zinc target by adopting a reactive magnetron sputtering method;
more specifically, the specific conditions of the reactive magnetron sputtering are as follows: background vacuum degree greater than 10-4Pa, using a pure metal target Zn; the working atmosphere is a mixed atmosphere of argon and oxygen, and the volume ratio of argon to oxygen is 2: 1; the sputtering pressure is 0.35 Pa; the sputtering power is 50-200W; in particular 140W;
the method for preparing the active metal doped dielectric layer is co-sputtering or reactive sputtering.
In particular, TaO doped with AgxThe film is deposited by adopting a silver target and tantalum oxide ceramic target co-sputtering method.
The specific conditions of the co-sputtering are as follows: background vacuum degree greater than 10-4Pa, using oxide ceramic target Ta2O5Co-sputtering with a metal target Ag; the working atmosphere is pure argon atmosphere; the sputtering pressure is 0.35 Pa; the sputtering power is 10-200W; in particular Ta2O5Target 90W and Ag target 10W;
the Al-doped ZnO is deposited by reactive sputtering in a way of placing a metal aluminum strip on a metal zinc target.
The specific conditions of the reactive sputtering are as follows: background vacuum degree greater than 10-4Pa using a metal target (Zn) doped with said active metal Al; the working atmosphere is a mixed atmosphere consisting of argon and oxygen; wherein the volume ratio of argon to oxygen is 2: 1; the sputtering pressure is 0.35 Pa; the sputtering power is 50-200W; in particular 140W;
the method further comprises the following steps: a step of coating a photoresist on the substrate before the photolithography, and stripping the photoresist after the deposition of the top electrode.
Specifically, the photoresist is a photoresist commonly used in the field;
and the stripping is to put the substrate on which the top electrode is deposited into acetone, remove the photoresist and complete the stripping.
In addition, the application of the resistive random access memory provided by the invention in storage and the application in the preparation of the memory also belong to the protection scope of the invention.
Compared with the prior art, the invention has the advantages that: the traditional resistive random access memory based on the active metal conductive filament uses active metal as an electrode, and controls the active metal to diffuse into a dielectric layer through an external electric field to form the on-off of the conductive filament so as to realize the resistive effect, wherein the formed conductive filament is often large in size and difficult to control; according to the invention, the active metal is added into the dielectric layer by a doping method, the doped oxide film is essentially used as an electrode, the undoped oxide film is used as the dielectric layer, an electron tunneling type conductive filament formed by active metal nanoclusters is favorably formed in the dielectric layer, the working current of the resistive random access memory can be effectively reduced, and the aim of low power consumption is further realized.
Drawings
Fig. 1 is a schematic structural diagram of a resistive random access memory device based on a partially active metal doped thin film according to the present invention, wherein the resistive random access memory device comprises a 1-substrate, a 2-bottom electrode, a 3-undoped dielectric layer, a 4-active metal doped dielectric layer, and a 5-top electrode.
Fig. 2 is an I-V characteristic curve of the resistive random access memory prepared in example 1.
Detailed Description
The present invention will be further illustrated with reference to the following specific examples, but the present invention is not limited to the following examples. The method is a conventional method unless otherwise specified. The starting materials are commercially available from the open literature unless otherwise specified. In the following examples, the thickness of the bottom electrode was 10 nm; the thickness of the top electrode is 50 nm; the substrates are commercial Pt (120 nm)/Ti (up to down to up15nm)/SiO2a/Si substrate with a thickness of 200 and 800 μm. The doping concentration of the active metal refers to the molar ratio of the active metal to the metal elements in the oxide, for example, 15% refers to the molar ratio of the active metal to the metal elements in the oxide of 15: 100.
Example 1 preparation of Pt/TaO operable at 1 μ A Limited Currentx:Ag/TaOxResistive random access memory with a/Pt structure.
Ultrasonically cleaning a substrate for 4-8 minutes by using acetone, alcohol and deionized water respectively, then drying the substrate by using nitrogen, photoetching a device pattern on the substrate by using an ultraviolet exposure machine, and putting primer into a vacuum chamber of a magnetron sputtering coating machine;
background vacuum pumping to 1 × 10-4And after Pa is less than or equal to Pa, starting coating.
Depositing Pt electrodes of the top electrode and the bottom electrode by adopting a direct-current magnetron sputtering platinum target; the specific conditions of the direct current magnetron sputtering are as follows: background vacuum degree of more than 10-4Pa, using a Pt target material of pure metal; the working atmosphere is pure argon atmosphere; the sputtering pressure is 0.35 Pa; the sputtering power is 30W;
undoped dielectric layer TaOxDepositing by adopting a radio frequency magnetron sputtering tantalum oxide ceramic target to obtain undoped TaOxA dielectric layer, the thickness of the layer being 20 nm; the specific conditions of the radio frequency magnetron sputtering are as follows: background vacuum degree of more than 10-4Pa, using oxide ceramic target Ta2O5(ii) a The working atmosphere is pure argon atmosphere; the sputtering pressure is 0.35 Pa; the sputtering power is 90W;
TaO doped with AgxThe film is deposited by adopting a silver target and tantalum oxide ceramic target co-sputtering method to obtain the TaO doped with active metal AgxA film dielectric layer, the doping concentration of Ag is 15%, TaO doped with active metal AgxThe thickness of the thin film dielectric layer is 20 nm; the specific conditions of the co-sputtering are as follows: background vacuum degree of more than 10-4Pa, oxide ceramic target Ta2O5Co-sputtering with a metal target Ag; the working atmosphere is pure argon atmosphere; the sputtering pressure is 0.35 Pa; sputtering power is Ta2O5Target 90W and Ag target 10W;
the multilayer film has clear and flat interface.
And after the coating is finished, turning off a power supply, filling nitrogen into a vacuum chamber of the magnetron sputtering coating machine until the pressure in the vacuum chamber is atmospheric pressure, opening the chamber, taking out a sample, and stripping to obtain the resistive random access memory device, wherein the section diagram of the device is shown in fig. 1. A schematic structural diagram of the resistive memory device with a part of active metal doped thin film obtained in this embodiment is shown in fig. 1. The resistive random access memory comprises a substrate 1, a bottom electrode 2, an undoped dielectric layer 3, an active metal doped dielectric layer 4 and a top electrode 5 from bottom to top in sequence.
Two wires are respectively led out from the bottom electrode and the top electrode (both Pt) to test the resistance change. Fig. 2 is an I-V characteristic curve of the resistive random access memory prepared in example 1. As can be seen from the figure, the device can realize nonvolatile resistance change behavior under the limiting current of 1 muA, and simultaneously can realize resistance change behavior under different limiting currents, the high resistance state is kept uniform, the low resistance state is reduced along with the increase of the limiting current, and the device has the potential of single-device multi-value storage.
Example 2: preparing the resistive random access memory with a Pd/ZnO/Al/ZnO/Pd structure.
Ultrasonically cleaning a substrate for 4-8 minutes by using acetone, alcohol and deionized water respectively, then drying the substrate by using nitrogen, photoetching a device pattern on the substrate by using an ultraviolet exposure machine, and putting primer into a vacuum chamber of a magnetron sputtering coating machine;
background vacuum pumping to 1 × 10-4And after Pa is less than or equal to Pa, starting coating.
Depositing Pd electrodes of the top electrode and the bottom electrode by adopting a direct-current magnetron sputtering platinum target; the specific conditions of the direct current magnetron sputtering are as follows: background vacuum degree of more than 10-4Pa, using a pure metal Pd target material; the working atmosphere is pure argon atmosphere; the sputtering pressure is 0.35 Pa; the sputtering power is 30W;
depositing ZnO by using a metal zinc target by adopting a reactive magnetron sputtering method to obtain an undoped ZnO dielectric layer, wherein the thickness of the layer is 20 nm; the specific conditions of the reactive magnetron sputtering are as follows: background vacuum degree of more than 10-4Pa, using a pure metallic Zn target material;the working atmosphere is a mixed atmosphere of argon and oxygen; the sputtering pressure is 0.35 Pa; the sputtering power is 140W;
performing reactive sputtering deposition on the Al-doped ZnO by placing a metal aluminum strip on a metal zinc target to obtain an active metal Al-doped ZnO film dielectric layer, wherein the doping concentration of Al is 15%, and the thickness of the active metal Al-doped AnO film dielectric layer is 20 nm; the specific conditions of the reactive sputtering are as follows: background vacuum degree of more than 10-4Pa using a target (Zn) doped with said active metal; the working atmosphere is a mixed atmosphere consisting of argon and oxygen; wherein the volume ratio of argon to oxygen is 2: 1; the sputtering pressure is 0.35 Pa; the sputtering power is 140W;
the prepared multilayer film has clear and flat interface.
And after the coating is finished, turning off a power supply, filling nitrogen into a vacuum chamber of the magnetron sputtering coating machine until the pressure in the vacuum chamber is atmospheric pressure, opening the chamber, taking out a sample, and stripping to obtain the resistive random access memory device, wherein the section diagram of the device is shown in fig. 1. The resistive random access memory comprises a substrate 1, a bottom electrode 2, an undoped dielectric layer 3, an active metal doped dielectric layer 4 and a top electrode 5 from bottom to top in sequence.
Two leads are respectively led out from the bottom electrode and the top electrode to test the resistance change.
Fig. 2 shows that the prepared resistive random access memory exhibits a stable bipolar resistive random behavior characteristic curve in direct-current voltage scanning, can normally work under the limiting current of 1 μ a, can normally work under 10 μ a, 100 μ a and 1mA, keeps the high-resistance state uniform, reduces the resistance of the low-resistance state along with the increase of the limiting current, and is expected to realize multi-value storage of five resistance states (4 low-resistance states and 1 high-resistance state) of a single device. According to the application, the active metal is transferred into the dielectric layer from the electrode in a doping mode, the regulation and control of the form of the conductive filament are realized, and the working current of the resistive random access memory is effectively reduced, so that the resistive random access memory improved by applying the technology disclosed by the invention is more beneficial to realizing the aim of low power consumption and is more suitable for practical application.

Claims (9)

1. A resistance change memory characterized in that: the resistive random access memory comprises a substrate, a bottom electrode, an undoped dielectric layer, an active metal doped dielectric layer and a top electrode from bottom to top in sequence.
2. The resistance change memory according to claim 1, characterized in that: the substrate is commercial Pt (120 nm)/Ti (15 nm)/SiO2a/Si substrate.
3. The resistance change memory according to claim 1 or 2, characterized in that: the bottom electrode and the top electrode are both selected from any one of inert metals; specifically, the metal is any one selected from Pt, Au and Pd;
the undoped dielectric layer is an oxide film; in the oxide thin film, the oxide is at least one selected from tantalum oxide, hafnium oxide and zinc oxide;
the active metal doped dielectric layer is an active metal doped oxide film; in the active metal doped oxide film, the oxide is selected from at least one of tantalum oxide, hafnium oxide and zinc oxide; the active metal is at least one of Ag, Cu, Al and Ru;
the doping concentration of the active metal is 5-20%.
4. The resistance change memory according to any one of claims 1 to 3, characterized in that: the thickness of the substrate is 200-800 μm;
the thickness of the bottom electrode is 5-100 nm;
the thickness of the undoped dielectric layer is 5-30 nm;
the thickness of the active metal doped dielectric layer is 5-30 nm;
the thickness of the top electrode is 5-100 nm.
5. A method for preparing the resistive random access memory according to any one of claims 1 to 4, comprising:
and after the dot array is manufactured on the substrate, photoetching is carried out, and then the bottom electrode, the undoped dielectric layer, the active metal doped dielectric layer and the top electrode are sequentially deposited to obtain the resistive random access memory.
6. The method of claim 5, wherein: the preparation method of the dot array is ultraviolet exposure or electron beam exposure;
the method for preparing the bottom electrode and the top electrode is direct-current magnetron sputtering;
the method for preparing the undoped dielectric layer is radio frequency magnetron sputtering or reactive magnetron sputtering;
the method for preparing the active metal doped dielectric layer is co-sputtering or reactive sputtering.
7. The method according to claim 5 or 6, characterized in that: the method further comprises the following steps: a step of coating a photoresist on the substrate before the photolithography, and stripping the photoresist after the deposition of the top electrode.
8. Use of a resistive random access memory according to any one of claims 1 to 4 for storage.
9. Use of the resistive random access memory according to any one of claims 1 to 4 in the preparation of a memory.
CN202010588247.5A 2020-06-24 2020-06-24 Resistive random access memory device structure based on partial active metal doped thin film and preparation method thereof Pending CN111725400A (en)

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Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
YIMING SUN 等: ""Cluster-Type Filaments Induced by Doping in Low-Operation-Current Conductive Bridge Random Access Memory"", 《ACS APPLIED MATERIALS & INTERFACES》 *

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Application publication date: 20200929