CN114429970A - Preparation method and structure of anti-radiation atomic switch device structure - Google Patents

Preparation method and structure of anti-radiation atomic switch device structure Download PDF

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CN114429970A
CN114429970A CN202210085596.4A CN202210085596A CN114429970A CN 114429970 A CN114429970 A CN 114429970A CN 202210085596 A CN202210085596 A CN 202210085596A CN 114429970 A CN114429970 A CN 114429970A
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metal electrode
barrier layer
radiation
depositing
sin
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CN114429970B (en
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许磊
魏敬和
刘国柱
赵伟
魏轶聃
魏应强
陈浩然
隋志远
周颖
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CETC 58 Research Institute
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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
    • H10B63/20—Resistance change memory devices, e.g. resistive RAM [ReRAM] devices comprising selection components having two electrodes, e.g. diodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof

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Abstract

The invention discloses a preparation method and a structure of a radiation-resistant atomic switch device structure, and belongs to the field of microelectronic and semiconductor devices. Providing an active metal electrode, and sequentially depositing SiN and SiO on the surface of the active metal electrode2(ii) a Photoetching and dry etching to form holes; depositing a barrier layer on the surface; preparing TaGeOx solid electrolytes with different components on the surface of the barrier layer; depositing an inert metal electrode by PVD, oxidizing the barrier layer to form a metal oxide in the process, and forming an alloy on the surface of the active metal electrode; etching areas on two sides of the opening, and then depositing a SiN protective layer on the whole surface; and connecting the active metal electrode with the inert metal electrode layer by adopting a dual damascene process. Compatible with CMOS process, high integration level, nonvolatile property, small size, high programming efficiency, high reliability, strong total dose resistance and the like, and is widely applied to high-speed, high-efficiency, high-integration level, nonvolatile and reconfigurable radiation-resistant FPGA (field programmable gate array), non-CMOS (complementary metal oxide semiconductor) processVolatile memory and bionic synapse device.

Description

Preparation method and structure of anti-radiation atomic switch device structure
Technical Field
The invention relates to the technical field of micro-electronics and semiconductor devices, in particular to a preparation method and a structure of a radiation-resistant atomic switch device structure.
Background
With the development of electronic systems towards multifunction, high speed, miniaturization and low power consumption required by various key projects in the fields of aviation, aerospace, ships, radars, strategic missiles, electronic countermeasure, communication and the like, the requirement on a high-reliability and radiation-resistant programmable logic device FPGA is more prominent. The traditional FPGA has the problems of poor radiation resistance, high power consumption, volatility (SRAM type), low speed, high programming voltage (Flash type), small scale (antifuse type) and the like, and a novel high-performance FPGA is urgently needed.
The atomic switch is used as a novel nonvolatile resistance change device, based on an Electrochemical Metallization (ECM) mechanism, Set and Reset operations are realized through formation and annihilation of metal conductive filaments, the atomic switch can be integrated in Cu interconnection through BEOL, and the atomic switch has the advantages of nonvolatility, small size, small on-resistance, high on-off ratio and the like, and meanwhile, the metal conductive filaments are used as conductive paths to enable the atomic switch to have stronger radiation resistance. The AS type FPGA is adopted, the advantages of SRAM type, Flash type and anti-fuse type FPGAs are integrated, the CMOS technology is compatible, the integration level is high, the advantages of high speed, high reliability, high programming efficiency and the like are achieved, the FPGA chip area can be obviously reduced, delay and power consumption are reduced, and the anti-radiation capability is strong.
Although AS devices are widely researched, the problems of device parameter consistency, reliability and the like still exist, which are closely related to cathode/anode electrodes, solid electrolyte materials and device structures of AS devices.
Disclosure of Invention
The invention aims to provide a preparation method and a structure of a radiation-resistant atomic switch device structure, so as to solve the problems in the background technology.
In order to solve the technical problem, the invention provides a preparation method of a radiation-resistant atomic switch device structure, which comprises the following steps:
step one, providing an active metal electrode, and depositing SiN and SiO on the surface of the active metal electrode in sequence2；
Step two, removing SiO on the surface by photoetching2Performing dry etching on the SiN to form an opening;
depositing a barrier layer on the surface;
preparing TaGeOx solid electrolytes with different components on the surface of the barrier layer;
depositing an inert metal electrode by PVD, oxidizing the barrier layer to form a metal oxide in the process, and forming an alloy on the surface of the active metal electrode;
etching the areas on the two sides of the opening, and then depositing an SiN protective layer on the whole surface;
and step six, connecting the active metal electrode with the inert metal electrode layer by adopting a dual damascene process.
Optionally, the metal element of the active metal electrode can satisfy an electrochemical metallization mechanism, including Cu, Ag, Al, Ti, or Zn;
the standard Gibbs free energy delta fG DEG generated by the metal oxide of the barrier layer is smaller than that of the oxide of the active electrode metal, and the metal selected for the barrier layer comprises Al, Ti, Ta, Zn and alloy formed by the Al, the Ti, the Ta and the Zn;
the metal elements of the inert metal electrode comprise Ru, Pt, W and Au.
Optionally, SiN and SiO are deposited2The process of (2) is PECVD, the thickness of SiN is 25nm, and SiO is2Is 150 nm.
Optionally, the aperture of the opening is 100 nm-1 um.
Optionally, the thickness of the barrier layer is 1nm to 4 nm.
Optionally, the process for preparing the TaGeOx solid electrolytes with different components comprises the following steps: adopting magnetron sputtering and utilizing Ta target material and Ge target material in O2And Ar2Alternately sputtering in atmosphere, and preparing TaGeOx solid electrolytes with different components by controlling the sputtering time of a Ta target and a Ge target or a Si target, wherein the thickness of the TaGeOx solid electrolyte is 20 nm-30 nm.
Optionally, the thickness of the inert metal electrode is 10-25 nm.
Optionally, in the fifth step, areas on two sides of the opening are etched, and the inert metal electrode, the TaGeOx solid electrolyte, and the barrier layer on two sides of the opening are removed by etching, so that the SiN on two sides of the opening is exposed.
The invention also provides a structure of a radiation-resistant atomic switch device, comprising:
an active metal electrode as an anode, a metal barrier layer, an oxide solid electrolyte layer, and an inert metal electrode as a cathode.
In the preparation method and the structure of the anti-radiation atomic switch device structure provided by the invention, the atomic switch device has the advantages of simple structure, compatibility with a CMOS (complementary metal oxide semiconductor) process, high integration level, non-volatility, small size, low on resistance, high on-off ratio, high programming efficiency, high reliability, strong total dose resistance and the like, and can be widely applied to the fields of high-speed, high-efficiency, high-integration level, non-volatility, reconfigurable anti-radiation FPGA, non-volatile memory, bionic synapse devices and the like.
Drawings
FIG. 1 is a schematic representation of SiN and SiO deposition on Cu interconnects2A process schematic diagram;
FIG. 2 is a schematic diagram of a photolithographic opening process;
FIG. 3 is a schematic view of a process for depositing a metal barrier layer;
FIG. 4 is a schematic diagram of a process for depositing an oxide solid electrolyte and inert metal electrodes;
FIG. 5 is a schematic diagram of a process for etching and depositing SiN;
FIG. 6 is a schematic diagram of a process for connecting an upper Cu interconnect to an inert metal electrode layer by a dual damascene process;
FIG. 7 is a schematic diagram of an atomic switching device employing a metal barrier layer according to the present invention;
FIG. 8 is a schematic diagram of a structure in which a metal barrier layer is oxidized to form a two-layer solid electrolyte after deposition of an oxide solid electrolyte;
FIG. 9 is a schematic diagram of the radiation-hard AS device Set process;
fig. 10 is a schematic diagram of a radiation-resistant AS device Reset process.
Detailed Description
The following will further describe the structure and the method for manufacturing the radiation-resistant atomic switching device structure in detail with reference to the accompanying drawings and specific embodiments. Advantages and features of the present invention will become apparent from the following description and from the claims. It is to be noted that the drawings are in a very simplified form and are not to precise scale, which is merely for the purpose of facilitating and distinctly claiming the embodiments of the present invention.
The invention provides a preparation process method of a radiation-resistant atomic switch device, which comprises the following steps:
in the first step, as shown in FIG. 1, Cu interconnection is used as an active metal electrode 1, and SiN 7 with a thickness of 25nm and SiO with a thickness of 150nm are sequentially deposited on the surface of the active metal electrode by PECVD (plasma enhanced chemical vapor deposition)28；
The metal element of the active metal electrode 1 is such that it satisfies the electrochemical metallization mechanism that when a positive voltage Vset is applied to the active metal electrode and the inert metal electrode is grounded, a reduction reaction (M) of the active metal ions occursn++ne-→ M), forming metal conductive filaments (Set process); when a negative voltage Vreset is applied to the active metal electrode, the metal atom M in the solid electrolyte undergoes an oxidation reaction to form Mn+(M-ne-→Mn+) The metal conductive filament dissolves (Reset process). In addition to CuThe metal electrode can also be Ag, Al, Ti or Zn;
second, as shown in FIG. 2, the SiO on the surface is removed by photolithography28, performing dry etching on the SiN 7 to form an opening with the aperture of 100 nm-1 um; .
Thirdly, as shown in fig. 3, depositing an Al barrier layer 2 on the surface by PVD with the deposition thickness of 1 nm-4 nm;
the standard gibbs free energy Δ fG ° of the metal oxide of the barrier layer is less than the oxide of the active electrode metal, thereby preventing the oxide solid electrolyte from causing oxidation of the active metal electrode during deposition. After the metal barrier layer is oxidized, the metal barrier layer and the electrolyte form a double-layer solid electrolyte with different metal ion mobility, and the consistency of electrical parameters is improved. At the BEOL process temperature, the metal barrier layer can form alloy on the surface of the active electrode, an alloy conductive filament is formed in the Set process, the stability of the conductive filament is improved, and the metal selected for the barrier layer comprises Al, Ti, Ta, Zn and the alloy formed by the Al, Ti, Ta and Zn;
fourthly, as shown in FIG. 4, magnetron sputtering is adopted, and Ta target and Ge target are used in O2And Ar2Alternately sputtering in atmosphere, controlling the sputtering time of Ta target and Ge target or Si target, preparing TaGeOx solid electrolyte 3 with different components, and depositing the thickness of 20 nm-30 nm; and then, depositing an inert metal electrode 4 by PVD with the thickness of 10-25 nm. The barrier metal Al is oxidized in the process to form solid electrolyte Al2O36, forming an alloy 5 on the surface of the Cu; the inert metal electrode has good conductivity, and the metal elements of the inert metal electrode comprise Ru, Pt, W and Au;
fifthly, as shown in fig. 5, etching the areas on the two sides of the opening, removing the inert metal electrodes, the TaGeOx solid electrolyte and the barrier layer on the two sides of the opening by etching, exposing the SiN on the two sides of the opening, and depositing a 15nm thick SiN protective layer by PECVD;
and sixthly, connecting the upper Cu interconnection with the inert metal electrode layer by adopting a dual damascene process as shown in FIG. 6.
Fig. 7 shows a structure of a radiation-resistant atomic switching device, which includes an active metal electrode 1, a metal barrier layer 2, a solid electrolyte layer 3, and an inert metal electrode 4. In this embodiment, the active metal electrode in the atomic switch is made of Cu, the metal barrier layer is made of Al, the solid electrolyte is made of TaGeOx, and the inert metal electrode is made of Ru. The metal barrier layer functions as: (1) at a certain temperature, alloy is formed on the surface of the active metal electrode, and an alloy conductive filament is formed in the Set process, so that the stability of the filament is improved; (2) prevent the oxidation of the active metal electrode caused in the deposition process of the oxide solid electrolyte; (3) the metal barrier layer is oxidized in the deposition process of the oxide solid electrolyte, so that double layers of solid electrolytes with different metal ion mobility are formed, and the parameter consistency of the device is improved. The TaGeOx solid electrolyte prepared by magnetron sputtering can improve the thermal stability of an atomic switch in the BEOL (Back End off line, BEOL) process thermal process.
As shown in FIG. 8, since the standard Gibbs free energy Δ fG generated by the oxide of Al should be smaller than that of Cu, the Al barrier layer protects the Cu electrode from being oxidized to form Cu during the deposition of TaGeOx solid electrolytexO to cause the surface of the Cu electrode to become rough, and more importantly, CuxO is difficult to reduce to Cu atoms during Set operation, which may result in reduced AS device yield. The Al barrier layer is oxidized to form Al2O3After 6, a two-layer solid electrolyte having a different Cu ion mobility may be formed with TaGeOx. Next, the Al barrier layer also forms an alloy layer 5 on the Cu surface.
As shown in FIG. 9, the atomic switch mainly utilizes the redox reaction of the active metal electrode to dominate the formation and annihilation M of the metal conductive filamentn++ne-And (4) working. When a positive voltage Vset is applied to the active metal electrode (anode) and the inert metal electrode (cathode) is grounded, the metal ions Mn+A reduction reaction (→ M) occurs to form a metal conductive filament. Because the alloy layer is formed on the surface of the Cu, Al atoms are doped into the formed Cu conductive filament, which is beneficial to improving the stability of the conductive filament.
As shown in fig. 10, after Reset operation, the conductive filament is preferentially dissolved and broken in the solid electrolyte with fast Cu ion diffusion rate, and the solid electrolyte with slow Cu ion diffusion rate may leave some Cu conductive filaments, which may play a role of electric field enhancement in the following Set process, and induce the conductive filament to nucleate and grow at the position, so as to reduce the randomness of conductive filament growth and improve the parameter consistency.
The above description is only for the purpose of describing the preferred embodiments of the present invention, and is not intended to limit the scope of the present invention, and any variations and modifications made by those skilled in the art based on the above disclosure are within the scope of the appended claims.

Claims (9)

1. A method for preparing a radiation-resistant atomic switch device structure is characterized by comprising the following steps:
step one, providing an active metal electrode, and depositing SiN and SiO on the surface of the active metal electrode in sequence2；
Step two, removing SiO on the surface by photoetching2Performing dry etching on the SiN to form an opening;
depositing a barrier layer on the surface;
preparing TaGeOx solid electrolytes with different components on the surface of the barrier layer;
depositing an inert metal electrode by PVD, oxidizing the barrier layer to form a metal oxide in the process, and forming an alloy on the surface of the active metal electrode;
etching the areas on the two sides of the opening, and then depositing an SiN protective layer on the whole surface;
and step six, connecting the active metal electrode with the inert metal electrode layer by adopting a dual damascene process.
2. The method of claim 1, wherein the metal element of the active metal electrode is capable of satisfying an electrochemical metallization mechanism, comprising Cu, Ag, Al, Ti, or Zn;
the standard Gibbs free energy delta fG DEG generated by the metal oxide of the barrier layer is smaller than that of the oxide of the active electrode metal, and the metal selected for the barrier layer comprises Al, Ti, Ta, Zn and alloy formed by the Al, the Ti, the Ta and the Zn;
the metal elements of the inert metal electrode comprise Ru, Pt, W and Au.
3. The method of claim 1, wherein the SiN and SiO deposition2The process of (2) is PECVD, the thickness of SiN is 25nm, and SiO is2Is 150 nm.
4. The method of claim 1, wherein the openings have a pore size of 100nm to 1 um.
5. The method of fabricating a radiation-resistant atomic switching device structure according to claim 1, wherein the thickness of the barrier layer is 1nm to 4 nm.
6. The method for preparing a radiation-resistant atomic switching device structure of claim 1, wherein the process for preparing TaGeOx solid electrolytes with different components comprises: adopting magnetron sputtering and utilizing Ta target material and Ge target material in O2And Ar2Alternately sputtering in atmosphere, and preparing TaGeOx solid electrolytes with different components by controlling the sputtering time of a Ta target and a Ge target or a Si target, wherein the thickness of the TaGeOx solid electrolyte is 20 nm-30 nm.
7. The method of claim 1, wherein the inert metal electrode has a thickness of 10 to 25 nm.
8. The method for preparing a radiation-resistant atomic switching device structure according to claim 1, wherein in the fifth step, areas on two sides of the opening are etched, and the inert metal electrode, the TaGeOx solid electrolyte and the barrier layer on two sides of the opening are removed by etching to expose the SiN on two sides of the opening.
9. A radiation-resistant atomic switching device structure, comprising:
an active metal electrode as an anode, a metal barrier layer, an oxide solid electrolyte layer, and an inert metal electrode as a cathode.
CN202210085596.4A 2022-01-25 2022-01-25 Preparation method and structure of anti-radiation atomic switch device structure Active CN114429970B (en)

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1889285A (en) * 2006-07-17 2007-01-03 南京大学 Non-volatile memory component based on RbAg4I5 film and producing method thereof
US20100102308A1 (en) * 2008-10-29 2010-04-29 Seagate Technology Llc Programmable resistive memory cell with oxide layer
CN104659208A (en) * 2015-02-05 2015-05-27 中国科学院微电子研究所 Non-volatile resistance random access memory and preparation method thereof
US20150364680A1 (en) * 2014-06-12 2015-12-17 Commissariat A L'energie Atomique Et Aux Energies Alternatives Resistive random access memory device
CN105990519A (en) * 2015-02-05 2016-10-05 中国科学院微电子研究所 Nonvolatile resistive random access memory device and preparation method thereof
KR20180000982A (en) * 2016-06-24 2018-01-04 고려대학교 세종산학협력단 Lanthanide metal buffer layer based atomic switch device
CN107732010A (en) * 2017-09-29 2018-02-23 华中科技大学 One kind gating tube device and preparation method thereof

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1889285A (en) * 2006-07-17 2007-01-03 南京大学 Non-volatile memory component based on RbAg4I5 film and producing method thereof
US20100102308A1 (en) * 2008-10-29 2010-04-29 Seagate Technology Llc Programmable resistive memory cell with oxide layer
US20150364680A1 (en) * 2014-06-12 2015-12-17 Commissariat A L'energie Atomique Et Aux Energies Alternatives Resistive random access memory device
CN104659208A (en) * 2015-02-05 2015-05-27 中国科学院微电子研究所 Non-volatile resistance random access memory and preparation method thereof
CN105990519A (en) * 2015-02-05 2016-10-05 中国科学院微电子研究所 Nonvolatile resistive random access memory device and preparation method thereof
KR20180000982A (en) * 2016-06-24 2018-01-04 고려대학교 세종산학협력단 Lanthanide metal buffer layer based atomic switch device
CN107732010A (en) * 2017-09-29 2018-02-23 华中科技大学 One kind gating tube device and preparation method thereof

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