CN107978557B - Method for manufacturing vacuum gap in etching groove - Google Patents

Method for manufacturing vacuum gap in etching groove Download PDF

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Publication number
CN107978557B
CN107978557B CN201711184301.4A CN201711184301A CN107978557B CN 107978557 B CN107978557 B CN 107978557B CN 201711184301 A CN201711184301 A CN 201711184301A CN 107978557 B CN107978557 B CN 107978557B
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oxide layer
vacuum gap
layer
etching groove
hydrofluoric acid
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CN107978557A (en
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邵克坚
乐陶然
曾明鑫
张彪
李元凯
刘欢
郭玉芳
程强
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Yangtze Memory Technologies Co Ltd
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Yangtze Memory Technologies Co Ltd
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/70Manufacture 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
    • H01L21/71Manufacture of specific parts of devices defined in group H01L21/70
    • H01L21/768Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
    • H01L21/76801Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the dielectrics, e.g. smoothing
    • H01L21/7682Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the dielectrics, e.g. smoothing the dielectric comprising air gaps
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
    • H01L21/3105After-treatment
    • H01L21/311Etching the insulating layers by chemical or physical means
    • H01L21/31105Etching inorganic layers
    • H01L21/31111Etching inorganic layers by chemical means

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  • Manufacturing & Machinery (AREA)
  • Power Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Computer Hardware Design (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Semiconductor Memories (AREA)
  • Drying Of Semiconductors (AREA)
  • Internal Circuitry In Semiconductor Integrated Circuit Devices (AREA)
  • Weting (AREA)

Abstract

The invention relates to a method for manufacturing a vacuum gap in an etching groove, which comprises the following steps: introducing hydrofluoric acid and ammonia gas into the etching groove, and removing the first oxide layer in the etching groove by controlling the concentration and the introduction rate of the introduced hydrofluoric acid and ammonia gas; and forming a linear second oxide layer at the top of the etching groove and forming a vacuum gap. According to the method for manufacturing the vacuum gap in the etching groove, the vacuum gap is manufactured among the metal copper, and the vacuum has the lowest dielectric constant, so that the capacitance among the copper layers can be greatly reduced, the leakage current phenomenon is reduced, the time-dependent dielectric breakdown characteristic is improved, and the performance of a device is improved. In addition, the invention does not adopt a plasma etching process when removing the oxide, so that the nitride layer can be well reserved while the oxide layer is eliminated, and the window formed by a new oxide layer is improved.

Description

Method for manufacturing vacuum gap in etching groove
Technical Field
The invention relates to a method for manufacturing a vacuum gap in an etching groove, and relates to the technical field of 3D NAND memory manufacturing.
Background
With the development of semiconductor technology, various semiconductor memory devices have been proposed. Semiconductor memory devices have advantages of fast access speed, high memory density, and the like, compared to conventional memory devices such as magnetic memory devices. Among these, the NAND structure is receiving more and more attention. To further increase memory density, a variety of three-dimensional (3D) NAND devices have emerged.
Fig. 1A-1F are schematic diagrams illustrating a process of forming a 3D NAND etched trench in the prior art. The method specifically comprises the following steps:
(1) as shown in fig. 1A, a standard film structure (film structure) is obtained after exposure on the basis of the initial structure, and includes a photoresist 1, a silicon oxynitride layer 2(SiON), an oxide layer 3, a tungsten layer 5, and a silicon carbonitride layer 4(SiCN) in this order from top to bottom.
(2) As shown in fig. 1B, the photoresist 1, the silicon oxynitride layer 2(SiON), and a part of the oxide layer 3 are removed by dry/wet etching, thereby exposing the tungsten layer 5.
(3) As shown in fig. 1C, a nitride layer 6 is deposited over the structure of step (2) by atomic layer deposition technique (ALD).
(4) As shown in fig. 1D, the nitride layer 6 on the oxide layer 3 and the nitride layer 6 on the tungsten layer 5 are removed by dry etching, but the nitride layer 6 on the side wall of the oxide layer 3 remains.
(5) As shown in fig. 1E, the structure obtained in step (4) is completely covered with metallic copper by Electroplating (ECP), forming a copper layer 7.
(6) As shown in fig. 1F, the top layer of copper metal is removed by Chemical Mechanical Polishing (CMP) until the top surfaces of the nitride layer 6 and the oxide layer 3 are exposed. Thus, through a plurality of steps, the etching groove structure can be finally obtained.
The following drawbacks exist during the above process: since the electroplating process can cause metal copper to diffuse in the nitride layer 6 and the oxide layer 3, the insulating property between every two copper layers 7 is affected, and current breaks down between the two copper layers 7 to form leakage current, so that the device performance is affected.
Disclosure of Invention
In order to solve the above technical problems, the present invention is directed to a method for manufacturing a vacuum gap in an etching trench, which is used to replace the isolation function of an oxide layer by manufacturing a vacuum gap in an etching trench structure, thereby solving the problem of copper diffusion and the problem of electrical leakage.
According to an aspect of the present invention, there is provided a method of manufacturing a vacuum gap in an etching bath, comprising the steps of:
introducing hydrofluoric acid and ammonia gas into the etching groove, and removing the first oxide layer in the etching groove by controlling the concentration and the introduction rate of the introduced hydrofluoric acid and ammonia gas;
and forming a linear second oxide layer at the top of the etching groove and forming a vacuum gap.
Preferably, the etching groove comprises a silicon nitride layer positioned at the bottom and a first oxide layer positioned above the silicon nitride layer, a plurality of conducting channels are distributed in the silicon nitride layer and the first oxide layer at intervals, the bottom of each conducting channel is provided with a conductor layer made of conducting materials, a copper layer is arranged on the conductor layer, and a nitride layer is arranged between the copper layer and the first oxide layer.
More preferably, the nitride layer is made of silicon nitride.
More preferably, the conductor layer is made of a conductive material.
Preferably, the conductive material comprises one or more of tungsten, cobalt, copper, aluminum and silicide.
Preferably, the first oxide layer is silicon dioxide.
Preferably, the second oxide layer is made of silicon dioxide.
Preferably, the hydrofluoric acid and the ammonia react with the first oxide layer to generate ammonium fluorosilicate and water, and the ammonium fluorosilicate and the water are pumped by the pumping equipment and discharged.
Preferably, the second oxide layer is formed by directly covering the prepared linear oxide on the top of the etching groove or by a slow-deposition film deposition process.
According to another aspect of the present invention, there is also provided a 3D NAND memory comprising etched trenches fabricated according to the above method.
The novel method for manufacturing the vacuum gap in the etching groove of the invention manufactures the vacuum gap between the metal copper, and the vacuum has the lowest dielectric constant, so the method can greatly reduce the capacitance between the copper layers, reduce the leakage current phenomenon, improve the time-dependent dielectric breakdown characteristic and further improve the performance of the device. In addition, the invention does not adopt a plasma etching process when removing the oxide, so that the nitride layer can be well reserved while the oxide layer is eliminated, and the window formed by a new oxide layer is improved.
Drawings
Various other advantages and benefits will become apparent to those of ordinary skill in the art upon reading the following detailed description of the preferred embodiments. The drawings are only for purposes of illustrating the preferred embodiments and are not to be construed as limiting the invention. Also, like reference numerals are used to refer to like parts throughout the drawings. In the drawings:
FIGS. 1A-1F are schematic diagrams of a prior art process for creating a vacuum gap in an etched trench;
FIGS. 2A-2B are schematic views of a process for forming a vacuum gap in an etch trench in accordance with the present invention;
FIG. 3 shows the elimination of an oxide layer (SiO) using hydrofluoric acid and ammonia gas according to the present invention2) Schematic diagram of the principle of (1).
Detailed Description
Embodiments of the present invention will now be described more fully hereinafter with reference to the accompanying drawings, in which preferred embodiments of the invention are shown. This invention may, however, be embodied in different forms and should not be construed as limited to the embodiments set forth herein. Like reference numerals refer to like elements throughout the specification.
It will be understood that, although the terms first, second, etc. may be used herein to describe various elements, these elements should not be limited by these terms. These terms are used to distinguish one element from another. For example, a first element could be termed a second element, and, similarly, a second element could be termed a first element, without departing from the scope of the present invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
It will be understood that when an element is referred to as being "on," "connected to" or "coupled to" another element, it can be directly on or connected or coupled to the other element or intervening elements may also be present. In contrast, when an element is referred to as being "directly on" or "directly connected to" or "directly coupled to" another element, there are no intervening elements present. Other words used to describe the relationship between elements should be interpreted in a similar manner (e.g., "between," "adjacent" with respect to "directly adjacent," etc.). When an element is referred to herein as being "on" or "under" another element, it can be directly coupled to the other element, or intervening elements may be present, or the elements may be separated by gaps or spaces.
The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise. It will be further understood that the terms "comprises," "comprising," "includes" and/or "including," when used herein, specify the presence of stated features, integers, steps, operations, elements, and/or components, but do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, and/or groups thereof.
The method for manufacturing the vacuum gap in the etching groove of the embodiment of the invention is applied to the current common etching groove structure. As shown in fig. 1F, the etching groove includes a silicon nitride carbide layer 4 at the bottom and a first oxide layer 3 on the silicon nitride carbide layer 4, a plurality of conductive channels are distributed at intervals in the silicon nitride carbide layer 4 and the first oxide layer 3, the bottom of the conductive channels is provided with a conductor layer 5 formed by a conductive material, the conductor layer 5 is provided with a copper layer 7, and a nitride layer 6 is arranged between the copper layer 7 and the first oxide layer 3. The nitride layer 6 may be made of silicon nitride.
In some embodiments, the conductor layer 5 in the etched trenches may be made of a conductive material, including but not limited to one or a combination of tungsten, cobalt, copper, aluminum, and silicide.
The process of manufacturing a vacuum gap in an etching tank according to an embodiment of the present invention is shown in fig. 2A-2B, and includes the following steps:
s1, as shown in fig. 2A, hydrofluoric acid and ammonia gas are introduced, and the first oxide layer (i.e., the oxide layer 3 in fig. 1A to 1F) in the etching trench is removed by controlling the concentration and the introduction rate of the introduced hydrofluoric acid and ammonia gas.
In this step the first oxide layer is removed and the nitride layer 6 is retained. Thus, a wider window is provided for the next step of forming a new oxide layer to cover.
In some embodiments, the first oxide layer is silicon dioxide. In some embodiments, the concentration of hydrofluoric acid is 1:500 (HF: H) by mass2O), the time of passage is from 1 to 5 minutes. And in the time of the buffer etching period, by controlling the dosage and the injection speed of hydrofluoric acid and ammonia gas, introducing the hydrofluoric acid and the ammonia gas into the surface of the first oxide layer to perform chemical reaction. In this process, the following chemical reaction processes occur gradually on the surface of the silica: SiO 22+4HF=SiF4+2H2O、SiO2+4HF+4NH3=SiF4+2H2O+4NH3、 SiF4+2HF+2NH3=(NH4)2SiF6. Finally, a solid-liquid mixture of ammonium fluorosilicate and water is produced. During the reaction, the solid-liquid mixture formed by the reaction is pumped away and discharged by a pumping device (such as a common vacuum pumping device) from time to time, and the process is repeated until the first oxide layer formed by the silicon dioxide is gradually corroded and disappears. In this process, since the nitride layer 6 does not chemically react with hydrofluoric acid or ammonia gas, it remains.
Because the ammonium fluosilicate generated by the reaction is quickly pumped away by a vacuum pumping device and the concentration of the hydrofluoric acid used by the method is low, the hydrofluoric acid etching process can easily remove the redundant oxide without damaging the nitride layer 6 which needs to be remained. The invention does not adopt the plasma etching process when removing the oxide, thereby well retaining the nitride layer while eliminating the oxide layer, and further improving the window formed by the new oxide layer.
S2, as shown in fig. 2B, the top of the etched trench is covered with the second oxide layer 8. The second oxide layer 8 is linear and extends continuously in the horizontal direction. The second oxide layer 8 is made of silicon dioxide.
In some embodiments, the second oxide layer 8 may be formed by directly covering the top of the etched trench with a prepared linear oxide, and then the space formed after the original first oxide layer 3 is etched is evacuated to form the vacuum gap 9. In other embodiments, the second oxide layer 8 may also be formed by a slow-deposition thin film deposition process including, but not limited to, Chemical Vapor Deposition (CVD), Physical Vapor Deposition (PVD), Atomic Layer Deposition (ALD), and/or other suitable methods.
In this way, a vacuum gap 9 is formed between the metallic copper layers 7 of the etched trench. Because the vacuum has the lowest dielectric constant, the invention can greatly reduce the capacitance between copper layers, reduce the leakage current phenomenon, improve the time-dependent dielectric breakdown characteristic and further improve the device performance.
The novel method for manufacturing the vacuum gap in the etching groove of the invention manufactures the vacuum gap between the metal copper, and the vacuum has the lowest dielectric constant, so the method can greatly reduce the capacitance between the copper layers, reduce the leakage current phenomenon, improve the time-dependent dielectric breakdown characteristic and further improve the performance of the device. In addition, the invention does not adopt a plasma etching process when removing the oxide, so that the nitride layer can be well reserved while the oxide layer is eliminated, and the window for depositing a new oxide layer is improved.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the appended claims.

Claims (7)

1. A method of forming a vacuum gap in an etch chamber, comprising the steps of:
introducing hydrofluoric acid and ammonia gas into the etching groove, removing the first oxide layer in the etching groove by controlling the concentration and the introduction rate of the introduced hydrofluoric acid and ammonia gas, reacting the hydrofluoric acid and ammonia gas with the first oxide layer to generate a solid-liquid mixture of ammonium fluosilicate and water, and pumping the solid-liquid mixture generated by the reaction away by extraction equipment in the reaction process; the etching groove comprises a silicon carbonitride layer positioned at the bottom and a first oxide layer positioned above the silicon carbonitride layer, a plurality of conductive channels are distributed in the silicon carbonitride layer and the first oxide layer at intervals, the bottoms of the conductive channels are provided with conductor layers made of conductive materials, copper layers are arranged on the conductor layers, and nitride layers are arranged between the copper layers and the first oxide layer;
forming a linear second oxide layer on the top of the etching groove and forming a vacuum gap; the second oxide layer is formed by directly covering the prepared linear oxide on the top of the etching groove or by a slow-deposition film deposition process.
2. A method of fabricating a vacuum gap in an etched trench as claimed in claim 1, wherein:
the nitride layer is made of silicon nitride.
3. A method of fabricating a vacuum gap in an etched trench as claimed in claim 1, wherein:
the conductor layer is made of a conductive material.
4. A method of fabricating a vacuum gap in an etched trench as claimed in claim 3, wherein:
the conductive material comprises one or more of tungsten, cobalt, copper, aluminum and silicide.
5. A method of fabricating a vacuum gap in an etched trench as claimed in claim 1, wherein:
the first oxide layer is silicon dioxide.
6. A method of fabricating a vacuum gap in an etched trench as claimed in claim 1, wherein:
the second oxide layer is made of silicon dioxide.
7. A 3D NAND memory characterized in that it comprises etched trenches manufactured according to the method of any one of claims 1 to 6.
CN201711184301.4A 2017-11-23 2017-11-23 Method for manufacturing vacuum gap in etching groove Active CN107978557B (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050012219A1 (en) * 2003-07-16 2005-01-20 Huey-Chiang Liou Air gap integration
CN101506955A (en) * 2006-09-21 2009-08-12 英特尔公司 Dielectric spacers for metal interconnects and method to form the same
US20160307773A1 (en) * 2015-04-15 2016-10-20 Samsung Electronics Co., Ltd. Method of Manufacturing Semiconductor Devices

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050012219A1 (en) * 2003-07-16 2005-01-20 Huey-Chiang Liou Air gap integration
CN101506955A (en) * 2006-09-21 2009-08-12 英特尔公司 Dielectric spacers for metal interconnects and method to form the same
US20160307773A1 (en) * 2015-04-15 2016-10-20 Samsung Electronics Co., Ltd. Method of Manufacturing Semiconductor Devices

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