CN109841566B - Semiconductor structure forming method and semiconductor structure - Google Patents

Semiconductor structure forming method and semiconductor structure Download PDF

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CN109841566B
CN109841566B CN201910089714.7A CN201910089714A CN109841566B CN 109841566 B CN109841566 B CN 109841566B CN 201910089714 A CN201910089714 A CN 201910089714A CN 109841566 B CN109841566 B CN 109841566B
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hole
layer
semiconductor structure
diffusion barrier
dielectric layer
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CN109841566A (en
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周烽
毛格
胡凯
万先进
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Yangtze Memory Technologies Co Ltd
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Yangtze Memory Technologies Co Ltd
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Abstract

The present invention relates to the field of semiconductor manufacturing technologies, and in particular, to a method for forming a semiconductor structure and a semiconductor structure. The forming method of the semiconductor structure comprises the following steps: providing a dielectric layer, wherein the dielectric layer is provided with a through hole which penetrates through the dielectric layer along a direction vertical to the dielectric layer; activating the surface of the side wall of the through hole to form an active bonding surface; and forming a diffusion barrier layer which at least covers the active bonding surface and is chemically bonded with the active bonding surface. The invention enhances the adhesiveness between the diffusion barrier layer and the side wall of the through hole and improves the performance of the semiconductor structure.

Description

Semiconductor structure forming method and semiconductor structure
Technical Field
The present invention relates to the field of semiconductor manufacturing technologies, and in particular, to a method for forming a semiconductor structure and a semiconductor structure.
Background
With the development of the planar flash memory, the manufacturing process of the semiconductor has been greatly improved. In recent years, however, the development of planar flash memories has met with various challenges: physical limits, existing development technology limits, and storage electron density limits, among others. In this context, to solve the difficulties encountered by flat flash memories and to pursue lower production costs of unit memory cells, various three-dimensional (3D) flash memory structures, such as 3D NOR (3D NOR) flash memory and 3D NAND (3D NAND) flash memory, have come into force.
The 3D NAND memory is based on the small volume and the large capacity, the design concept of the three-dimensional mode layer-by-layer stacking height integration of the storage units is adopted, the memory with high unit area storage density and high-efficiency storage unit performance is produced, and the mainstream process of the design and production of the emerging memory is formed.
The through hole process is an important process for realizing the electrical connection between different layers in semiconductor structures such as a three-dimensional memory. However, in the conventional via process, the metal layer at the bottom of the via is easy to diffuse along the sidewall of the via, which seriously affects the yield and reliability of the semiconductor structure.
Therefore, how to avoid the diffusion of the conductive layer along the sidewall of the through hole, increase the yield of the semiconductor structure, and improve the performance of the semiconductor structure is a technical problem to be solved urgently.
Disclosure of Invention
The invention provides a semiconductor structure and a forming method thereof, which are used for solving the problem of poor performance of the conventional semiconductor structure.
In order to solve the above problems, the present invention provides a method for forming a semiconductor structure, comprising the steps of:
providing a dielectric layer, wherein the dielectric layer is provided with a through hole which penetrates through the dielectric layer along a direction vertical to the dielectric layer;
activating the surface of the side wall of the through hole to form an active bonding surface;
and forming a diffusion barrier layer which at least covers the active bonding surface and is chemically bonded with the active bonding surface.
Preferably, the specific step of activating the sidewall surface of the through-hole includes:
and transmitting activated gas into the through hole, wherein the activated gas reacts with the dielectric layer positioned on the side wall to generate an active bonding surface with bonding groups.
Preferably, the step of forming a diffusion barrier layer at least covering the active bonding surface and chemically bonded to the active bonding surface includes:
delivering a precursor gas into the through hole, wherein the precursor gas is chemically bonded with the bonding group so as to be adsorbed on the active bonding surface;
and transmitting reaction gas into the through hole, wherein the reaction gas reacts with the precursor gas adsorbed on the active bonding surface to form the diffusion barrier layer.
Preferably, the dielectric layer is made of silicon dioxide; the specific steps of delivering the activated gas into the through-hole include:
and transmitting nitrogen and hydrogen into the through hole in a plasma environment to generate an active bonding surface with amino.
Preferably, the precursor gas is tungsten fluoride.
Preferably, the reaction gas is ammonia or nitrogen.
Preferably, the method further comprises the following steps after the diffusion barrier layer is formed:
and depositing a conductive material in the through hole to form a conductive plug.
Preferably, the diffusion barrier layer covers the active bonding surface and the bottom surface of the through hole;
the bottom end of the through hole is provided with a conductive layer;
the conductive plug is electrically connected to the conductive layer through the diffusion barrier layer.
In order to solve the above problem, the present invention also provides a semiconductor structure comprising:
the dielectric layer is provided with a through hole penetrating through the dielectric layer along a direction perpendicular to the dielectric layer;
an active bonding surface formed by activating a sidewall surface of the through-hole;
and the diffusion barrier layer at least covers the active bonding surface and is chemically bonded with the active bonding surface.
Preferably, the active bonding surface comprises a bonding group;
the diffusion barrier layer is chemically bonded to the bonding group.
Preferably, the dielectric layer is made of silicon dioxide;
the bonding group is an amino group.
Preferably, the material of the diffusion barrier layer is tungsten nitride.
Preferably, the method further comprises the following steps:
and the conductive plug is filled in the through hole and covers the surface of the diffusion barrier layer.
Preferably, the method further comprises the following steps:
the conducting layer is positioned at the bottom end of the through hole;
the diffusion impervious layer covers the surface of the active bonding surface and the bottom surface of the through hole, and the conductive plug is electrically connected with the conductive layer through the diffusion impervious layer.
Preferably, the method further comprises the following steps:
and the through hole penetrates through the dielectric layer and the insulating layer simultaneously.
According to the forming method of the semiconductor structure and the semiconductor structure, the active bonding surface is formed by activating the surface of the side wall of the through hole, the adhesion between the diffusion barrier layer and the side wall of the through hole is enhanced by utilizing the chemical bonding between the active bonding surface and the diffusion barrier layer, the conductive layer particles at the bottom of the through hole are effectively prevented from diffusing along the interface between the diffusion barrier layer and the side wall, the performance of the semiconductor structure is improved, and the yield and the reliability of the semiconductor structure are improved.
Drawings
FIG. 1 is a flow chart of a method of forming a semiconductor structure in accordance with an embodiment of the present invention;
FIGS. 2A-2D are schematic cross-sectional views of the main processes for forming a semiconductor structure in accordance with an embodiment of the present invention;
FIG. 3 is a structural formula of a material forming an active bonding surface in an embodiment of the present invention;
FIG. 4 is a chemical reaction formula of a material forming an active bonding surface reacting with a precursor gas in an embodiment of the present invention;
FIG. 5A is a graph illustrating the results of a control wafer lift-off test of a semiconductor structure formed in accordance with an embodiment of the present invention;
FIG. 5B is a graph illustrating the result of lift-off of an overlay mark on a semiconductor structure formed in accordance with an embodiment of the present invention;
FIG. 5C is a graph illustrating results of in-line defect characterization of a semiconductor structure formed in accordance with an embodiment of the present invention;
figure 6 is a schematic cross-sectional view of a semiconductor structure in accordance with an embodiment of the present invention.
Detailed Description
The following describes a method for forming a semiconductor structure and a semiconductor structure according to embodiments of the present invention in detail with reference to the accompanying drawings.
In the manufacturing process of the through hole of the semiconductor structure, a dielectric layer is usually etched to the surface of a conductive layer positioned at the bottom end of the dielectric layer to form a through hole penetrating through the dielectric layer; then forming a diffusion barrier layer on the surface of the side wall of the through hole; and finally, filling a conductive material into the through hole to form a conductive plug covering the surface of the diffusion barrier layer, wherein the end part of the conductive plug is electrically connected with the conductive layer through the diffusion barrier layer, so that the transmission of an electric signal is realized. Wherein the diffusion barrier layer is used for preventing the particles in the conductive layer from diffusing along the side wall of the through hole.
However, since the metal material such as copper has strong diffusion performance, the conventional diffusion barrier layer made of titanium nitride material is difficult to effectively block the particles in the conductive layer from diffusing along the sidewall of the through hole, so that the performance of the semiconductor structure formed thereby is not good. In view of this, tungsten nitride materials are increasingly being used to form diffusion barriers instead of titanium nitride materials. Although the tungsten nitride material has a good effect of blocking diffusion of the conductive layer particles, the tungsten nitride material has poor adhesion with the dielectric layer, and the conductive layer particles may still diffuse along the interface between the diffusion barrier layer and the dielectric layer, thereby limiting the application of the conductive layer particles in the via manufacturing process.
In order to improve the adhesion between the diffusion barrier layer and the dielectric layer at the sidewall of the through hole and prevent the conductive layer particles from diffusing along the interface between the diffusion barrier layer and the dielectric layer, thereby improving the performance of the semiconductor structure, the present embodiment provides a method for forming a semiconductor structure, fig. 1 is a flow chart of a method for forming a semiconductor structure in the embodiment of the present invention, and fig. 2A to 2D are schematic diagrams of main process cross-sections of the semiconductor structure in the forming process in the embodiment of the present invention. The semiconductor structure described in this embodiment may be any structure that requires a via hole to be provided and a conductive plug to be filled in the via hole to achieve electrical connection between different layers, such as a three-dimensional semiconductor structure (which may be, but is not limited to, a 3D NAND memory). As shown in fig. 1 and fig. 2A to fig. 2D, the method for forming a semiconductor structure according to this embodiment includes the following steps:
step S11, providing a dielectric layer 20, where the dielectric layer 20 has a through hole 21 penetrating through the dielectric layer 20 along a direction perpendicular to the dielectric layer 20, as shown in fig. 2A.
Specifically, the bottom end of the through hole 21 has a conductive layer 22, and the material of the conductive layer 22 may be a metal material such as copper. The specific steps of forming the through hole 21 may include: firstly, forming an insulating layer 23 on the surface of the conducting layer 22 and forming a dielectric layer 20 on the surface of the insulating layer 23; then, etching the dielectric layer 20 by using the insulating layer 23 as an etching stop layer and adopting a first etching process to form the through hole 21 penetrating through the dielectric layer 20 along a direction perpendicular to the dielectric layer 20; and then, etching the insulating layer 23 along the through hole 21 by using a second etching process, so that the through hole 21 extends to the surface of the conductive layer 22, that is, the through hole 21 simultaneously penetrates through the dielectric layer 20 and the insulating layer 23. The material of the insulating layer 23 may be a nitride material, such as silicon nitride.
Step S12, the sidewall surface of the through hole 21 is activated to form an active bonding surface 24, as shown in fig. 2B.
Preferably, the specific step of activating the sidewall surface of the through-hole 21 includes:
and transmitting activated gas into the through hole 21, wherein the activated gas reacts with the dielectric layer 20 positioned on the side wall to generate an active bonding surface with bonding groups.
Specifically, before the sidewall surface of the through hole 21 is activated, the sidewall surface of the through hole 21 may be cleaned to reduce impurity particles. By transmitting the activated gas into the through hole 21 and reasonably selecting the type and the activation condition of the activated gas, the activated gas and the dielectric layer 20 forming the side wall of the through hole 21 are subjected to chemical reaction to generate a bonding group which is easily bonded with the material forming the diffusion barrier layer.
The dielectric layer 20 is made of silicon dioxide, and fig. 3 is a structural formula of a material forming an active bonding surface according to an embodiment of the present invention. The specific steps of delivering the activated gas into the through-hole 21 include:
and transmitting nitrogen and hydrogen into the through hole 21 in a plasma environment to generate an active bonding surface with amino.
As shown in FIG. 3, nitrogen and hydrogen react with the silicon dioxide material forming the dielectric layer 20 under plasma environment to generate amino groups bonded to silicon atoms in the silicon dioxide, i.e., a large amount of Si-NH is formed on the sidewall surface of the through hole 212Chemical bond.
When the insulating layer 23 made of silicon nitride or the like is further disposed on the lower surface of the dielectric layer 20, the insulating layer 23 forming the sidewall of the through hole 21 may react with nitrogen and hydrogen in a plasma environment to generate Si — NH2Chemical bonds, i.e. Si-NH2The chemical bonds are distributed throughout the sidewalls of the via 21.
Step S13, forming a diffusion barrier layer 25 covering at least the active bonding surface 24 and chemically bonded to the active bonding surface 24, as shown in fig. 2C.
Preferably, the step of forming the diffusion barrier layer 25 at least covering the active bonding surface 24 and chemically bonded to the active bonding surface 24 includes:
delivering a precursor gas into the through hole 21, the precursor gas chemically bonding with the bonding group to adsorb to the active bonding surface 24;
and transmitting a reaction gas into the through hole 21, wherein the reaction gas reacts with the precursor gas adsorbed on the active bonding surface 24 to form the diffusion barrier layer 25.
Specifically, during the process of depositing the diffusion barrier layer 25 on the sidewall surface, the precursor gas for forming the diffusion barrier layer 25 is bonded with the bonding group exposed on the sidewall surface of the through hole 21 through a chemical reaction, so that adsorption of the precursor gas on the sidewall surface is promoted, the finally deposited diffusion barrier layer 25 is chemically connected with the sidewall of the through hole 21, the adhesion between the diffusion barrier layer 25 and the dielectric layer 20 is significantly enhanced, particles in the conductive layer 22 are prevented from diffusing along the interface between the diffusion barrier layer 25 and the dielectric layer 20, and thus the electrical performance of the semiconductor structure is effectively improved.
The specific thickness of the diffusion barrier layer 25 to be formed may be selected by those skilled in the art according to actual needs, and in order to reduce the contact resistance between the diffusion barrier layer 25 and the conductive plug 26 to be formed subsequently, the thickness of the diffusion barrier layer 25 is preferably 1nm to 5 nm.
Fig. 5A is a graph of control wafer lift-off test results for a semiconductor structure formed in accordance with an embodiment of the present invention, fig. 5B is a graph of overlay mark lift-off results for a semiconductor structure formed in accordance with an embodiment of the present invention, and fig. 5C is a graph of online defect characterization results for a semiconductor structure formed in accordance with an embodiment of the present invention. As can be seen from fig. 5A, 5B, and 5C, the semiconductor structure formed in this embodiment mode is greatly improved in the number of defects.
In the following description, the material of the diffusion barrier layer 25 is exemplified by tungsten nitride, and fig. 4 is a chemical reaction formula of a reaction between a material forming an active bonding surface and a precursor gas in the embodiment of the present invention. The specific step of forming a diffusion barrier layer 25 at least covering the active bonding surface 24 and chemically bonded to the active bonding surface 24 comprises:
(1) transmitting tungsten fluoride gas into the through hole 21, the tungsten fluoride gas and amino (-NH) in the active bonding surface 242) A chemical reaction occurs as shown in figure 4, allowing the fluorinationTungsten atoms in tungsten are bonded with nitrogen atoms in amino groups, and hydrogen fluoride gas is generated at the same time, so that the bonding of silicon atoms in the dielectric layer 20 and tungsten atoms in tungsten fluoride is indirectly realized.
(2) And transmitting ammonia gas or nitrogen gas into the through hole 21, wherein the ammonia gas or nitrogen gas reacts with the tungsten fluoride bonded on the active bonding surface 24 through a chemical bond to generate tungsten nitride.
Preferably, the step of forming the diffusion barrier layer 25 further includes:
depositing a conductive material in the via 21 to form a conductive plug 26, as shown in fig. 2D.
Wherein the conductive material may be, but is not limited to, tungsten.
Preferably, the diffusion barrier layer 25 covers the active bonding surface 24 and the bottom surface of the through hole 21;
the bottom end of the through hole 21 is provided with a conducting layer 22;
the conductive plug 26 is electrically connected to the conductive layer 22 through the diffusion barrier layer 25.
Specifically, the diffusion barrier layer 25 is conductive, and signal transmission between the conductive layer 22 and the conductive plug 26 is achieved through the diffusion barrier layer 25.
Furthermore, the present embodiment provides a semiconductor structure, and fig. 6 is a schematic cross-sectional view of the semiconductor structure according to the present embodiment. The semiconductor structure provided by the present embodiment can be formed by the method shown in fig. 1 and fig. 2A to 2D. As shown in fig. 1, fig. 2A to fig. 2D, and fig. 6, the semiconductor structure provided in the present embodiment includes:
the dielectric layer 20 is provided with a through hole 21 penetrating through the dielectric layer 20 along a direction perpendicular to the dielectric layer 20;
an active bonding face 24 formed by activating a sidewall surface of the through-hole 21;
and the diffusion barrier layer 25 at least covers the active bonding surface 24 and is chemically bonded with the active bonding surface 24.
Preferably, the active bonding surface 24 includes a bonding group;
the diffusion barrier layer 25 is chemically bonded to the bonding group.
Preferably, the material of the dielectric layer 20 is silicon dioxide;
the bonding group is an amino group.
Preferably, the material of the diffusion barrier layer 25 is tungsten nitride.
Preferably, the semiconductor structure further comprises:
and the conductive plug 26 is filled in the through hole 21 and covers the surface of the diffusion barrier layer 25.
Preferably, the semiconductor structure further comprises:
a conductive layer 22 at the bottom end of the via hole 21;
the diffusion barrier layer 25 covers the active bonding surface 24 and the bottom surface of the through hole 21, and the conductive plug 26 is electrically connected with the conductive layer 22 through the diffusion barrier layer 25.
Preferably, the semiconductor structure further comprises:
and the insulating layer 23 is positioned between the dielectric layer 20 and the conducting layer 22, and the through hole 21 simultaneously penetrates through the dielectric layer 20 and the insulating layer 23.
According to the semiconductor structure and the method for forming the same provided by the specific embodiment, the active bonding surface is formed by activating the surface of the side wall of the through hole, and the active bonding surface is chemically bonded with the diffusion barrier layer, so that the adhesion between the diffusion barrier layer and the side wall of the through hole is enhanced, the conductive layer particles at the bottom of the through hole are effectively prevented from diffusing along the interface between the diffusion barrier layer and the side wall, the performance of the semiconductor structure is improved, and the yield and the reliability of the semiconductor structure are improved.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (11)

1. A method for forming a semiconductor structure, comprising the steps of:
providing a dielectric layer, wherein the dielectric layer is provided with a through hole which penetrates through the dielectric layer along a direction vertical to the dielectric layer;
transmitting activated gas into the through hole, wherein the activated gas reacts with the dielectric layer positioned on the side wall of the through hole to generate an active bonding surface with bonding groups;
forming a diffusion barrier layer at least covering the active bonding surface and chemically bonded with the active bonding surface to enhance the adhesion between the diffusion barrier layer and the dielectric layer;
the dielectric layer is made of silicon dioxide; the specific steps of delivering the activated gas into the through-hole include: transmitting nitrogen and hydrogen into the through hole in the plasma environment to generate Si-NH on the surface of the side wall of the through hole2Chemical bonds, constituting an active bonding surface.
2. The method for forming a semiconductor structure according to claim 1, wherein the step of forming a diffusion barrier layer at least covering the active bonding surface and chemically bonded to the active bonding surface comprises:
delivering a precursor gas into the through hole, wherein the precursor gas is chemically bonded with the bonding group so as to be adsorbed on the active bonding surface;
and transmitting reaction gas into the through hole, wherein the reaction gas reacts with the precursor gas adsorbed on the active bonding surface to form the diffusion barrier layer.
3. The method of claim 2, wherein the precursor gas is tungsten fluoride.
4. The method of claim 3, wherein the reactive gas is ammonia or nitrogen.
5. The method of claim 1, further comprising the steps of, after forming the diffusion barrier layer:
and depositing a conductive material in the through hole to form a conductive plug.
6. The method of forming a semiconductor structure according to claim 5, wherein the diffusion barrier layer covers the active bonding face and a bottom face of the via;
the bottom end of the through hole is provided with a conductive layer;
the conductive plug is electrically connected to the conductive layer through the diffusion barrier layer.
7. A semiconductor structure, comprising:
the dielectric layer is provided with a through hole penetrating through the dielectric layer along a direction perpendicular to the dielectric layer, and the dielectric layer is made of silicon dioxide;
an active bonding surface formed by activating the sidewall surface of the through-hole, wherein the activation of the sidewall surface of the through-hole forms Si-NH2Chemical bonds forming an active bonding surface with bonding groups;
and the diffusion barrier layer at least covers the active bonding surface and is chemically bonded with the bonding group so as to enhance the adhesion between the diffusion barrier layer and the dielectric layer.
8. The semiconductor structure of claim 7, wherein the material of the diffusion barrier layer is tungsten nitride.
9. The semiconductor structure of claim 7, further comprising:
and the conductive plug is filled in the through hole and covers the surface of the diffusion barrier layer.
10. The semiconductor structure of claim 9, further comprising:
the conducting layer is positioned at the bottom end of the through hole;
the diffusion impervious layer covers the active bonding surface and the bottom surface of the through hole, and the conductive plug is electrically connected with the conductive layer through the diffusion impervious layer.
11. The semiconductor structure of claim 10, further comprising:
and the through hole penetrates through the dielectric layer and the insulating layer simultaneously.
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CN112899615B (en) * 2019-11-19 2023-02-21 长鑫存储技术有限公司 Film forming method and semiconductor device manufacturing method
CN112864089A (en) * 2019-11-27 2021-05-28 长鑫存储技术有限公司 Semiconductor structure and preparation method of interconnection structure
CN112366195B (en) * 2020-10-10 2022-02-22 长江存储科技有限责任公司 Bonding method and bonding structure

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