CN116387147B - Dielectric film, manufacturing method thereof and conductive plug - Google Patents
Dielectric film, manufacturing method thereof and conductive plug Download PDFInfo
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- CN116387147B CN116387147B CN202310645608.9A CN202310645608A CN116387147B CN 116387147 B CN116387147 B CN 116387147B CN 202310645608 A CN202310645608 A CN 202310645608A CN 116387147 B CN116387147 B CN 116387147B
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 24
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 83
- 239000010703 silicon Substances 0.000 claims abstract description 83
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 83
- 239000000463 material Substances 0.000 claims abstract description 74
- 239000011737 fluorine Substances 0.000 claims abstract description 49
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 49
- 239000004065 semiconductor Substances 0.000 claims description 44
- 239000000758 substrate Substances 0.000 claims description 40
- 239000007789 gas Substances 0.000 claims description 32
- 239000000126 substance Substances 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 28
- 239000002243 precursor Substances 0.000 claims description 23
- 150000001875 compounds Chemical class 0.000 claims description 20
- 239000012621 metal-organic framework Substances 0.000 claims description 14
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- 239000013310 covalent-organic framework Substances 0.000 claims description 12
- 229920000642 polymer Polymers 0.000 claims description 11
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 9
- 238000000151 deposition Methods 0.000 claims description 7
- 238000010574 gas phase reaction Methods 0.000 claims description 7
- -1 alkyl compound Chemical class 0.000 claims description 6
- 229910044991 metal oxide Inorganic materials 0.000 claims description 5
- 150000004706 metal oxides Chemical class 0.000 claims description 5
- 239000000178 monomer Substances 0.000 claims description 5
- 239000011148 porous material Substances 0.000 claims description 5
- 235000012239 silicon dioxide Nutrition 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 239000012071 phase Substances 0.000 claims 1
- 239000012808 vapor phase Substances 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 27
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 8
- 230000015572 biosynthetic process Effects 0.000 abstract description 7
- 230000008569 process Effects 0.000 description 12
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 8
- 239000004020 conductor Substances 0.000 description 8
- 230000004888 barrier function Effects 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 5
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 description 5
- 230000009471 action Effects 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 238000002161 passivation Methods 0.000 description 4
- 230000005684 electric field Effects 0.000 description 3
- 230000010354 integration Effects 0.000 description 3
- 239000013110 organic ligand Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000007740 vapor deposition Methods 0.000 description 3
- 239000013474 COF-1 Substances 0.000 description 2
- 239000013475 COF-5 Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 239000013148 Cu-BTC MOF Substances 0.000 description 2
- 239000013132 MOF-5 Substances 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 239000013207 UiO-66 Substances 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 239000003989 dielectric material Substances 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
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- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 150000002460 imidazoles Chemical class 0.000 description 2
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- 229910052751 metal Inorganic materials 0.000 description 2
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- 238000009832 plasma treatment Methods 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- LJUQGASMPRMWIW-UHFFFAOYSA-N 5,6-dimethylbenzimidazole Chemical compound C1=C(C)C(C)=CC2=C1NC=N2 LJUQGASMPRMWIW-UHFFFAOYSA-N 0.000 description 1
- 208000011380 COVID-19–associated multisystem inflammatory syndrome in children Diseases 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- ZWAJLVLEBYIOTI-UHFFFAOYSA-N cyclohexene oxide Chemical compound C1CCCC2OC21 ZWAJLVLEBYIOTI-UHFFFAOYSA-N 0.000 description 1
- FWFSEYBSWVRWGL-UHFFFAOYSA-N cyclohexene oxide Natural products O=C1CCCC=C1 FWFSEYBSWVRWGL-UHFFFAOYSA-N 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- NBBQQQJUOYRZCA-UHFFFAOYSA-N diethoxymethylsilane Chemical compound CCOC([SiH3])OCC NBBQQQJUOYRZCA-UHFFFAOYSA-N 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- WMIYKQLTONQJES-UHFFFAOYSA-N hexafluoroethane Chemical compound FC(F)(F)C(F)(F)F WMIYKQLTONQJES-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000013315 hypercross-linked polymer Substances 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000002319 photoionisation mass spectrometry Methods 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 235000013824 polyphenols Nutrition 0.000 description 1
- 239000003361 porogen Substances 0.000 description 1
- 229940079877 pyrogallol Drugs 0.000 description 1
- 238000002310 reflectometry Methods 0.000 description 1
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical compound FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 description 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
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- 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
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment 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
- H01L21/3105—After-treatment
- H01L21/3115—Doping the insulating layers
-
- 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
- H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
- H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
- H01L21/76801—Applying 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
- H01L21/76822—Modification of the material of dielectric layers, e.g. grading, after-treatment to improve the stability of the layers, to increase their density etc.
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/52—Arrangements for conducting electric current within the device in operation from one component to another, i.e. interconnections, e.g. wires, lead frames
- H01L23/522—Arrangements for conducting electric current within the device in operation from one component to another, i.e. interconnections, e.g. wires, lead frames including external interconnections consisting of a multilayer structure of conductive and insulating layers inseparably formed on the semiconductor body
- H01L23/532—Arrangements for conducting electric current within the device in operation from one component to another, i.e. interconnections, e.g. wires, lead frames including external interconnections consisting of a multilayer structure of conductive and insulating layers inseparably formed on the semiconductor body characterised by the materials
- H01L23/5329—Insulating materials
Abstract
The application provides a dielectric film, a manufacturing method thereof and a conductive plug. The dielectric film includes a non-silicon-based dielectric film and fluorine radicals doped into the non-silicon-based dielectric film. The dielectric property of the film layer is related to the polarity of the material forming the film layer, that is, the polarity of the material is larger, the dielectric constant of the film layer is smaller, on the basis of the dielectric property, after fluorine radicals with low polarity groups are doped in the non-silicon-based dielectric film with low dielectric constant, the fluorine radicals can increase the hydrophobicity of the film layer material, so that the reaction between the film layer material and moisture in the air is reduced, the formation of high polarity groups such as hydroxyl groups is further reduced, and the fluorine radicals are low polarity groups, so that the influence of the fluorine radicals on the dielectric property of the non-silicon-based dielectric film is smaller, and the dielectric film can reach the theoretical minimum k value.
Description
Technical Field
The application relates to the technical field of semiconductor manufacturing, in particular to a dielectric film, a manufacturing method thereof and a conductive plug.
Background
With the continuous improvement of chip integration, RC delay, crosstalk noise, power consumption and the like become more serious problems. Low k (Low dielectric constant) technology is being generated in such a background and is increasingly applied to integrated circuit fabrication processes.
As the process node advances below 10 and nm, conventional F-SiO 2 New materials such as MOF (metal organic framework compound), COF (covalent organic framework compound), PIM (microporous polymer) and the like have been attracting attention from the productivity community because OSG and P-OSG have failed to meet the demands. The porous material has a porous structure, which increases the specific surface area of the material, and the k value of air is close to 1, so that the k value can be effectively reduced, however, the moisture in the air is difficult to contact, the moisture reacts with the material to generate high-polarity groups such as hydroxyl, and the high-polarity groups can affectThe dielectric properties of the material are loud, making it often difficult for the material to reach its theoretical minimum k value. For example, the theoretical value of the MOF material is mostly smaller than 2, and the actual value is mostly around 2.3.
Disclosure of Invention
The present application provides a dielectric film, a method for fabricating the same and a conductive plug, which solve the problem that the material with low dielectric constant is difficult to reach the theoretical minimum k value in the prior art.
In order to achieve the above object, according to one aspect of the present application, there is provided a dielectric film including a non-silicon-based dielectric film and fluorine radicals doped into the non-silicon-based dielectric film.
Further, the material of the non-silicon-based dielectric film includes any one of a metal organic framework compound, a covalent organic framework compound, or a microporous polymer.
Further, the thickness of the dielectric film is 150 nm-250 nm.
In order to achieve the above object, according to one aspect of the present application, there is provided a method of manufacturing a dielectric film, the method comprising the steps of: providing a semiconductor substrate, wherein the semiconductor substrate is provided with a first surface; forming a non-silicon-based dielectric film on the first surface; fluorine radicals are doped in the non-silicon-based dielectric film to form a dielectric film.
Further, the step of forming a non-silicon-based dielectric film includes: depositing a layer of precursor material on the first surface; the semiconductor substrate with the precursor material layer and the organic gas source are placed into a chemical vapor reaction chamber, and a chemical vapor method is adopted to enable the organic gas source and the precursor material layer to react to form the non-silicon-based dielectric film.
Further, the material of the precursor material layer includes one or more of a metal oxide, an organic monomer, an alkyl compound, or an aryl compound.
Further, the step of forming the dielectric film includes: providing a fluoride having fluorine radicals; a chemical vapor process is employed to react the fluoride with the non-silicon based dielectric film to form a dielectric film.
Further, the fluoride includes perfluoroalkanes.
According to another aspect of the present application, there is provided a conductive plug including: a semiconductor substrate having a first surface; the dielectric film is arranged on the first surface, the dielectric film is provided with a second surface far away from the first surface, and the dielectric film is provided with a groove penetrating from the second surface to the first surface; and the conductive connecting part is arranged in the groove to form a conductive plug.
Further, the semiconductor body includes a silicon substrate, silicon dioxide and silicon carbonitride which are stacked, and the dielectric film is disposed in contact with the silicon carbonitride.
By applying the technical scheme of the application, the dielectric film is formed by doping fluorine free radicals into the non-silicon-based dielectric film after the non-silicon-based dielectric film with low dielectric constant is formed. Because the dielectric property of the film layer is related to the polarity of the material forming the film layer, i.e. the higher the polarity of the material, the lower the dielectric constant of the film layer, on the basis of which, after fluorine radicals with low polarity groups are doped in the non-silicon-based dielectric film with low dielectric constant, the fluorine radicals can increase the hydrophobicity of the film layer material, thereby reducing the reaction of the film layer material with moisture in the air, further reducing the formation of high polarity groups such as hydroxyl groups, and the fluorine radicals are basically low polarity groups, therefore, the influence of the fluorine radicals on the dielectric property of the non-silicon-based dielectric film is smaller, and the dielectric film can reach the theoretical minimum k value.
Drawings
The accompanying drawings, which are included to provide a further understanding of the application and are incorporated in and constitute a part of this specification, illustrate embodiments of the application and together with the description serve to explain the application. In the drawings:
fig. 1 is a schematic cross-sectional view showing a method for manufacturing a dielectric film according to an embodiment of the application, wherein a precursor material layer is formed;
FIG. 2 is a schematic cross-sectional view of a dielectric film formed on a non-silicon substrate according to one embodiment of the present application;
FIG. 3 is a schematic cross-sectional view showing a dielectric film formed by the method of fabricating a dielectric film according to an embodiment of the present application;
FIG. 4 shows a schematic cross-sectional structure of a conductive plug;
FIG. 5 is a schematic cross-sectional view showing a mask layer formed on a side of the dielectric film shown in FIG. 3 away from the semiconductor substrate in order to form the conductive plugs shown in FIG. 4;
FIG. 6 is a schematic diagram showing a cross-sectional structure of a groove etched on the basis of that shown in FIG. 5;
fig. 7 is a schematic cross-sectional structure of filling the grooves shown in fig. 6 with a conductive material.
Wherein the above figures include the following reference numerals:
1. a semiconductor substrate; 2. a precursor material layer; 3. a non-silicon-based dielectric film; 4. a dielectric film; 5. a mask layer; 6. a groove; 7. a conductive material; 8. a conductive connection portion; 9. a barrier layer.
Detailed Description
It should be noted that, without conflict, the embodiments of the present application and features of the embodiments may be combined with each other. The application will be described in detail below with reference to the drawings in connection with embodiments.
In order that those skilled in the art will better understand the present application, a technical solution in the embodiments of the present application will be clearly and completely described below with reference to the accompanying drawings in which it is apparent that the described embodiments are only some embodiments of the present application, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the present application without making any inventive effort, shall fall within the scope of the present application.
It should be noted that the terms "first," "second," and the like in the description and the claims of the present application and the above figures are used for distinguishing between similar objects and not necessarily for describing a particular sequential or chronological order. It is to be understood that the data so used may be interchanged where appropriate in order to describe the embodiments of the application herein. Furthermore, the terms "comprises," "comprising," and "having," and any variations thereof, are intended to cover a non-exclusive inclusion, such that a process, method, system, article, or apparatus that comprises a list of steps or elements is not necessarily limited to those steps or elements expressly listed but may include other steps or elements not expressly listed or inherent to such process, method, article, or apparatus.
As mentioned in the background art, as the integration level of chips is continuously improved, the problems of RC delay, crosstalk noise, power consumption, etc. of chips are more and more serious, and in order to improve the problems, the Low k (Low dielectric constant) technology is applied to the integrated circuit manufacturing process in the prior art, so that the formed Low dielectric material layer can improve the problems. However, in the manufacturing process of forming the low dielectric material layer, the material is often inevitably contacted with air, so that moisture in the air reacts with the material, and further high polar groups such as hydroxyl groups are generated, and the polar groups can affect the dielectric properties of the material, so that the material often has difficulty in reaching the theoretical minimum k value. In order to solve the above technical problems, the applicant of the present application provides a dielectric film, a method for manufacturing the same, and a conductive plug.
According to one embodiment of the present application, a dielectric film is provided that includes a non-silicon-based dielectric film and fluorine radicals doped into the non-silicon-based dielectric film.
By adopting the technical scheme, the fluorine free radicals are doped into the non-silicon-based dielectric film after the non-silicon-based dielectric film with low dielectric constant is formed, so that the dielectric film is formed. Because the dielectric property of the film layer of the dielectric film is related to the polarity of the material forming the film layer, namely the larger the polarity of the material is, the smaller the dielectric constant of the film layer is, on the basis of the dielectric property, after fluorine radicals with low polarity groups are doped in the non-silicon-based dielectric film with low dielectric constant, the fluorine radicals can increase the hydrophobicity of the film layer material, so that the reaction between the film layer material and moisture in the air is reduced, the formation of high polarity groups such as hydroxyl groups is further reduced, and the fluorine radicals are low polarity groups, so that the influence of the fluorine radicals on the dielectric property of the non-silicon-based dielectric film is smaller, the dielectric film can reach the theoretical minimum k value, and the problems of RC time delay, crosstalk noise, power consumption and the like of a chip can be better solved.
In some alternative embodiments, the material of the non-silicon-based dielectric film includes any one of a metal organic framework compound, a covalent organic framework compound, or a microporous polymer.
In the above embodiment, with the increasing chip integration, semiconductor system Cheng Jiedian is advanced to below 10nm, and conventional fluorine-containing silicon dioxide (F-SiO 2 ) The problems of serious RC delay, crosstalk noise, power consumption and the like are brought to the silicon oxide glass (OSG) and the phosphorus-containing silicon oxide glass (P-OSG), so that any one of the metal organic framework compound, the covalent organic framework compound or the microporous polymer is adopted, and the porous structure improves the specific surface area of the material because the material is a porous material, and the dielectric constant value of the material can be effectively reduced because the dielectric constant value of air is close to 1. Exemplary, the metal organic framework compounds described above may include MOF-5, HKUST-1, UIO-66, and the like, where MOF-5 refers to the presence of Zn 2+ And terephthalic acid (H) 2 BDC) is a three-dimensional framework with a micropore structure, which is formed by connecting a central metal ion and an organic ligand through an octahedron form; HKUST-1 is organic ligand 1,3, 5-pyrogallol and metal ion Cu 2+ Combining to form a blue cubic crystal copper-based ultra-microporous metal framework (MOF); UIO-66, chemical formula C 48 H 28 O 32 Zr 6 Zr is used as a metal center, and terephthalic acid (H) 2 BDC) is a rigid metal-organic framework material of an organic ligand, the covalent organic framework compound may include COF-1, COF-5, etc., wherein COF-1 and COF-5 are both two COFs obtained by self-polymerization of boric acid and polycondensation of boric acid and a polyphenol compound, and the microporous polymer may include self-polymerization microporous Polymer (PIMS), super-crosslinked polymer (HCPs), etc. Optionally, dopeFluorine radicals to the non-silicon based dielectric film may replace hydrogen atoms on benzene rings in the non-silicon based dielectric film and/or adsorb to the material surface in the form of-CxFy.
In order to provide better uniformity and better stability of the dielectric film, in some alternative embodiments, the thickness of the dielectric film is 150nm to 250nm.
In other alternative embodiments, applicants of the present application further provide a method of making a dielectric film comprising: providing a semiconductor substrate, wherein the semiconductor substrate is provided with a first surface; forming a non-silicon-based dielectric film on the first surface; fluorine radicals are doped in the non-silicon-based dielectric film to form a dielectric film.
According to the manufacturing method, the non-silicon-based dielectric film with low dielectric constant is formed on the first surface of the semiconductor substrate, so that the non-silicon-based dielectric film is used for improving the problems of RC time delay, crosstalk noise, power consumption and the like of chips in an integrated circuit, and further, fluorine radicals are introduced into the non-silicon-based dielectric film to change the hydrophilicity of the non-silicon-based dielectric film, so that fluorine radicals are doped into the non-silicon-based dielectric film, the fluorine radicals increase the hydrophobicity of the non-silicon-based dielectric film, a dielectric film is formed, compared with the non-silicon-based dielectric film, the high-polarity groups formed by contact of surface materials and moisture in the air are fewer, the influence on the dielectric property of the materials is reduced, and because the fluorine radicals are low-polarity groups, the influence of the fluorine radicals on the dielectric property of the non-silicon-based dielectric film is smaller, so that the dielectric film reaches the theoretical minimum k value, and the problems of RC time delay, the crosstalk noise, the power consumption and the like of the chips can be better solved.
Exemplary embodiments of a method of fabricating a dielectric film according to the present application will be described in more detail below. These exemplary embodiments may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. It should be appreciated that these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the concept of these exemplary embodiments to those skilled in the art.
In some alternative embodiments, as shown in fig. 1, the step of forming the non-silicon-based dielectric film 3 includes: depositing a layer 2 of precursor material on a first surface, wherein the semiconductor substrate 1 has the above-mentioned first surface; as shown in fig. 2, a semiconductor substrate 1 having a precursor material layer and an organic gas source are placed in a chemical vapor reaction chamber, and a chemical vapor process is employed to react the organic gas source and the precursor material layer to form a non-silicon-based dielectric film 3.
In the above embodiment, in order to form the non-silicon-based dielectric film 3, a precursor material is first prepared, and then the precursor material is deposited on the first surface of the semiconductor substrate 1 to form a precursor material layer, and the semiconductor substrate 1 on which the precursor material layer is deposited is placed in a chemical vapor reaction chamber, while an organic gas source is introduced into the chemical vapor reaction chamber, so that the organic gas source and the precursor material layer undergo a vapor reaction, thereby converting the precursor material layer into the non-silicon-based dielectric film 3, as shown in fig. 2.
Wherein, the formation process of the chemical vapor method uses heat with higher pressure, so that a more reproducible film can be generated, and the thickness of the film can be controlled by the time/power of the reaction process, thereby realizing the controllability of the thickness of the film, and leading the formed non-silicon-based dielectric film 3 to have higher stoichiometry and higher density.
Alternatively, as shown in fig. 2, the chemical vapor process includes plasma-enhanced chemical vapor deposition, and in order to form the low-dielectric, non-silicon-based dielectric film 3 on the semiconductor substrate 1, the organic gas source may be a gas source including silane (SiH (CH) 3 ） 3 ) Trimethylsilyl (3 MS, (CH) 3 ） 3 SiH), diethoxymethylsilane (DEMS, si (C) 2 H 5 O） 2 CH 3 H) And cyclohexene oxide (CHO, C 6 H 10 O) any one or more of. By adopting the organic gas source as a source material, firstly, the ionization of the organic gas source is called plasma by the action of an externally added electric field in a plasma chemical gas phase reaction chamber,because the plasma is in a mixed aggregate form composed of electrons, positive ions and neutral particles, the particles can be continuously collided, further the organic gas source is ionized to form a large number of ionized particles of the organic gas source and a large number of active groups with higher free energy, further complex reactions are carried out among other surrounding active groups, gas molecules without the active groups or groups thereof, the reaction proceeds to the direction of the active groups required by deposition, the active groups required by deposition and the gas molecules which are not activated yet expand to the surface of the precursor material layer, and then the reaction with the precursor material layer can be carried out, so that islands can be connected with adjacent islands through continuous growth, and further continuous films can be formed, and the films are the non-silicon-based dielectric films 3.
In some alternative embodiments, the material of the precursor material layer includes one or more of a metal oxide, an organic monomer.
Specifically, in the above embodiment, one or more of the metal oxide and the organic monomer may be reacted as a precursor material and an organic gas source, so as to form any one of a metal organic framework compound, a covalent organic framework compound, or a microporous polymer, which may be the non-silicon-based dielectric film, wherein the metal oxide may include an oxide of zinc (Zn), an oxide of iron (Fe), an oxide of indium (In), an oxide of cobalt (Co), an oxide of copper (Cu), an oxide of zirconium (Zr), an oxide of manganese (Mn), an oxide of lithium (Li), an oxide of cadmium (Cd), and an oxide of mercury (Hg); the organic monomer may include carboxylic acids and imidazole compounds, wherein the carboxylic acids may be aryl compounds, and the aryl compounds may include terephthalic acid, trimesic acid, and the like, and the imidazole compounds may be alkyl compounds, and the alkyl compounds may include 2-methylimidazole, 5, 6-dimethylbenzimidazole, and the like, as examples.
In some alternative embodiments, as shown in fig. 3, the step of forming the dielectric film 4 includes: providing a fluoride having fluorine radicals; a chemical vapor process is employed to react the fluoride with a non-silicon-based dielectric film on the semiconductor substrate 1 to form the dielectric film 4.
In the above embodiment, since the fluorine radicals are relatively reactive and unstable, in order to dope the fluorine radicals in the non-silicon-based dielectric film, it is necessary to provide a fluoride having fluorine radicals so that the fluoride can provide the fluorine radicals to the non-silicon-based dielectric film, so that the fluorine radicals can be separated in the chemical vapor reaction chamber after the above fluoride and the non-silicon-based dielectric film are put into the chemical vapor reaction chamber, and thus can be diffused to the surface of the non-silicon-based dielectric film after being deposited on the surface of the non-silicon-based dielectric film, thereby forming the above dielectric film 4.
Specifically, the chemical vapor process may include a plasma enhanced chemical vapor deposition process. For example, in order to form the dielectric film 4, a bias voltage of 40 to 60w is first applied so that the formed air plasma cleans the chemical vapor reaction chamber and the glass for plasma treatment for at least 30 minutes, thereby removing the perfluoroalkane film that may be formed on the inner surface of the reaction chamber or the glass in the previous experiment; then placing the non-silicon-based dielectric film into the chemical vapor reaction chamber and applying vacuum until the pressure in the reaction chamber is less than or equal to 0.20mbar for at least 30 minutes, thereby removing water that may be adsorbed on the non-silicon-based dielectric film; further, a perfluoroalkane gas can be introduced to make the perfluoroalkane gas enter the chemical gas phase reaction chamber, and the internal pressure of the perfluoroalkane gas can meet the pressure within the specification range of the mass flow controller by adjusting a regulator of the chemical gas phase reaction chamber, and a proper amount of perfluoroalkane gas is arranged in the chemical gas phase reaction chamber, so that the pressure required by an experiment is maintained; further, the above-mentioned perfluoroalkane gas can form plasma under the action of external electric field, optionally, a radio frequency generator can be used to ignite the plasma, and an L-C matching unit can be used to adjust radio frequency, so as to maximize radio frequency power and reduce reflectivity of the film, and the frequency of the above-mentioned radio frequency generator can be 13.56MHz, for example. So that fluorine radicals generated from the perfluoroalkane gas can react with the non-silicon-based dielectric film to form the dielectric film 4 under the action of the plasma, and after the dielectric film 4 is formed, the residual perfluoroalkane gas is discharged from the reaction chamber and discharged to normal pressure, and finally the semiconductor substrate 1 having the dielectric film 4 is taken out from the chemical vapor reaction chamber.
Further, as shown in fig. 3, the semiconductor substrate 1 with the dielectric film 4 after the treatment may be placed in an oven at 100-140 ℃ to remove unreacted perfluoroalkane gas, and then the treated dielectric film 4 may be placed in a dryer to prevent the dielectric film 4 from adsorbing water from the atmosphere. After the above-mentioned treatment of perfluoroalkane plasma vapor deposition (PECVD), the contact angle of the formed dielectric film 4 is 115 ° to 130 °, whereas the contact angle of the non-silicon-based dielectric film subjected to the treatment of perfluoroalkane plasma vapor deposition (PECVD) is 55 ° to 65 °, so that it is known that the film material can be changed from a hydrophilic material to a hydrophobic material by the treatment of perfluoroalkane plasma vapor deposition (PECVD).
In order that the fluoride provides fluorine radicals that are not subjected to H or C x H y Interference of free radicals, since perfluoroalkanes to F-containing, H-free, in some alternative embodiments, the fluoride selected comprises perfluoroalkanes. Illustratively, the above-mentioned perfluoroalkanes include perfluoromethane or perfluoroethane.
In other alternative embodiments, applicants of the present application further provide a conductive plug, as shown in FIG. 4, comprising: a semiconductor substrate 1, the semiconductor substrate 1 having a first surface; the dielectric film 4 in the above embodiment or the dielectric film 4 formed by the manufacturing method in the above another embodiment, the dielectric film 4 is disposed on the first surface of the semiconductor substrate 1, the dielectric film 4 has a second surface far from the first surface, and the dielectric film 4 has a groove penetrating from the second surface to the first surface; and the conductive connecting part 8 is arranged in the groove to form a conductive plug. Optionally, the conductive plug may further include a barrier layer 9, where the barrier layer 9 is disposed between the conductive connection portion 8 and the dielectric film 4 or between the conductive connection portion 8 and the semiconductor substrate 1.
In the above embodiment, as shown in fig. 5, in order to form the conductive plug, first, a mask layer 5 is formed on the side of the dielectric film 4 away from the semiconductor substrate 1. Further, as shown in fig. 6, the mask layer 5 and the dielectric film 4 are sequentially etched until the semiconductor substrate 1 is exposed, thereby forming a recess 6. Further, as shown in fig. 7, the grooves formed by the semiconductor substrate 1, the dielectric film 4 and the mask layer 5 are filled with a conductive material 7 by depositing the conductive material 7 in the grooves such that the conductive material 7 covers the surface of the mask away from the dielectric film 4. Further, as shown in fig. 4, the mask layer on the side of the dielectric film 4 away from the semiconductor substrate 1 and a portion of the conductive material located outside the recess are removed by chemical mechanical polishing, and the remaining portion of the conductive material forms the conductive connection portion 8, thereby forming the conductive plug, wherein in some alternative embodiments, the conductive plug further includes a barrier layer 9, where the barrier layer 9 may be deposited on the sidewall and the bottom of the recess after the recess is formed, and the conductive material is formed on the side of the barrier layer 9 away from the semiconductor substrate 1, the side away from the dielectric film 4, and the side away from the mask layer, so that the barrier layer 9 is disposed between the conductive connection portion 8 and the dielectric film 4 or between the conductive connection portion 8 and the semiconductor substrate 1, for preventing the material diffusion of the conductive connection portion 8 from causing electric leakage, preventing formation of a spike, and the like.
In the above embodiments, the conductive plug has the dielectric film described in the above embodiments, because the dielectric property of the film layer of the dielectric film is related to the polarity of the material forming the film layer, that is, the greater the polarity of the material, the smaller the dielectric constant of the film layer, based on which, after doping fluorine radicals with low polarity groups in the low dielectric constant non-silicon-based dielectric film, the fluorine radicals can increase the hydrophobicity of the film layer material, thereby reducing the reaction of the film layer material with moisture in the air, further reducing the formation of high polarity groups such as hydroxyl groups, and the fluorine radicals are low polarity groups, so that the effect of the fluorine radicals on the dielectric property of the non-silicon-based dielectric film is small, thereby enabling the dielectric film to reach the theoretical minimum k value, and further being capable of better solving the problems of RC delay, crosstalk noise, power consumption and the like of the chip, so that the conductive plug with the dielectric film has wider application.
In some alternative embodiments, the semiconductor body includes a silicon substrate, a passivation layer, and an etch stop layer in a stacked arrangement. Illustratively, the passivation layer comprises silicon dioxide and the etch stop layer comprises silicon carbonitride, the dielectric film being located on a side of the etch stop layer remote from the passivation layer.
In the above embodiment, the silicon dioxide is used as the passivation layer on the surface of the silicon substrate, so that the silicon device is prevented from being polluted, scratched and the like, and the durability of the wafer in the production and manufacturing process is enhanced; the silicon carbide nitride is used as an etching stop layer in the subsequent production and manufacturing flow, so that the etching precision is accurately controlled.
The above dielectric film and the method of manufacturing the same according to the present application will be further described with reference to examples and comparative examples.
Example 1
The embodiment provides a manufacturing method of a dielectric film, which comprises the following steps:
providing a semiconductor substrate, wherein the semiconductor substrate is provided with a first surface;
forming a non-silicon-based dielectric film on the first surface;
using a bias voltage of 50W to allow the formed air plasma to clean the chemical vapor reaction chamber and glassware for plasma treatment for 30 minutes;
placing the non-silicon-based dielectric film into the chemical vapor reaction chamber and applying vacuum until the pressure in the reaction chamber is less than or equal to 0.20mbar for 30 minutes;
introducing a perfluoroalkane gas to enable the perfluoroalkane gas to enter a chemical gas phase reaction chamber;
applying an external electric field to the chemical gas phase reaction chamber filled with the perfluoroalkyl gas to form plasma, igniting the plasma by using a radio frequency generator, and adjusting the radio frequency to 13.56MHz by using an L-C matching unit;
under the action of the plasma, enabling fluorine radicals generated from the perfluoroalkane gas to react with the non-silicon-based dielectric film to form a dielectric film;
and (3) discharging the residual perfluoroalkane gas out of the reaction chamber, discharging the perfluoroalkane gas to normal pressure, and finally taking out the dielectric film from the chemical vapor reaction chamber.
Comparative example 1
The comparative example provides a method for manufacturing a dielectric film, comprising the following steps:
providing a semiconductor substrate, depositing a dielectric substrate forming material and a sacrificial or unstable pore forming material on the semiconductor substrate to form a pore-forming agent-containing film;
converting the porogen-containing film into a porous low-k dielectric film using a curing process;
the porous dielectric film with low dielectric constant is placed in an aqueous medium to introduce hydroxyl (OH) and/or hydrogen (H) groups, thereby completing the introduction of active bonding and obtaining the final dielectric film.
The dielectric constants of the dielectric films in the above examples and comparative examples were tested, and the test procedures and results were as follows:
the dielectric films of examples and comparative examples were respectively made into a first metal-dielectric film-semiconductor structure capacitance and a second metal-dielectric film-semiconductor structure capacitance, so that the first metal-dielectric film-semiconductor structure capacitance and the second metal-dielectric film-semiconductor structure capacitance were measured by using an impedance analyzer to obtain corresponding C-V characteristic curves, and dielectric constants of the dielectric films were calculated as shown in table 1:
TABLE 1
Thus, the dielectric constant of the dielectric film formed by the embodiment is closer to the theoretical value of the dielectric film.
From the above description, it can be seen that the above embodiments of the present application achieve the following technical effects:
the dielectric film is formed by doping fluorine radicals into the above-mentioned non-silicon-based dielectric film after forming the non-silicon-based dielectric film of low dielectric constant. Because the dielectric property of the film layer of the dielectric film is related to the polarity of the material forming the film layer, namely the larger the polarity of the material is, the smaller the dielectric constant of the film layer is, on the basis of the dielectric property, after fluorine radicals with low polarity groups are doped in the non-silicon-based dielectric film with low dielectric constant, the fluorine radicals can increase the hydrophobicity of the film layer material, so that the reaction between the film layer material and moisture in the air is reduced, the formation of high polarity groups such as hydroxyl groups is further reduced, and the fluorine radicals are low polarity groups, so that the influence of the fluorine radicals on the dielectric property of the non-silicon-based dielectric film is smaller, the dielectric film can reach the theoretical minimum k value, and the problems of RC time delay, crosstalk noise, power consumption and the like of a chip can be better solved.
The above description is only of the preferred embodiments of the present application and is not intended to limit the present application, but various modifications and variations can be made to the present application by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application should be included in the protection scope of the present application.
Claims (9)
1. A dielectric film comprising a non-silicon-based dielectric film and fluorine radicals doped into the non-silicon-based dielectric film, wherein the material of the non-silicon-based dielectric film comprises any one of a metal organic framework compound containing benzene rings, a covalent organic framework compound containing benzene rings, or a microporous polymer containing benzene rings, and wherein the metal organic framework compound, the covalent organic framework compound, and the microporous polymer are porous materials, and the fluorine radicals are used for replacing hydrogen atoms on the benzene rings.
2. The dielectric film of claim 1, wherein the dielectric film has a thickness of 150nm to 250nm.
3. A method for producing a dielectric film, comprising the steps of:
providing a semiconductor substrate, wherein the semiconductor substrate is provided with a first surface;
forming a non-silicon-based dielectric film on the first surface;
doping fluorine radicals in the non-silicon-based dielectric film to form the dielectric film;
the material of the non-silicon-based dielectric film comprises any one of a metal organic framework compound containing benzene ring, a covalent organic framework compound containing benzene ring or a microporous polymer containing benzene ring, wherein the metal organic framework compound, the covalent organic framework compound and the microporous polymer are porous materials, and fluorine free radicals are used for replacing hydrogen atoms on the benzene ring.
4. The method of claim 3, wherein the step of forming the non-silicon-based dielectric film comprises:
depositing a layer of precursor material on the first surface;
and placing the semiconductor substrate with the precursor material layer and an organic gas source into a chemical gas phase reaction chamber, and adopting a chemical gas phase method to enable the organic gas source and the precursor material layer to react to form the non-silicon-based dielectric film.
5. The method of claim 4, wherein the precursor material layer comprises one or more of a metal oxide, an organic monomer, an alkyl compound, or an aryl compound.
6. The method of any one of claims 3 to 5, wherein the step of forming the dielectric film comprises:
providing a fluoride having said fluorine radicals;
and adopting a chemical vapor phase method to enable the fluoride and the non-silicon-based dielectric film to react to form the dielectric film.
7. The method of claim 6, wherein the fluoride comprises a perfluoroalkane.
8. A conductive plug, comprising:
a semiconductor body having a first surface;
the dielectric film of claim 1 or 2, or a dielectric film formed by the method of any one of claims 3 to 7, the dielectric film being disposed on the first surface, the dielectric film having a second surface remote from the first surface, and the dielectric film having a recess extending from the second surface to the first surface;
and the conductive connecting part is arranged in the groove to form the conductive plug.
9. The conductive plug of claim 8, wherein the semiconductor body comprises a silicon substrate, silicon dioxide, and silicon carbonitride in a stacked arrangement, the dielectric film being disposed in contact with the silicon carbonitride.
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| CN104637961A (en) * | 2013-11-13 | 2015-05-20 | 联华电子股份有限公司 | Semiconductor structure and manufacturing method thereof |
| CN110100296A (en) * | 2017-10-18 | 2019-08-06 | 株式会社爱发科 | Ion source and ion implantation apparatus |
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| CN1610076A (en) * | 2003-06-30 | 2005-04-27 | 松下电器产业株式会社 | Method for forming ferroelectric film and semiconductor device |
| CN1790632A (en) * | 2004-12-16 | 2006-06-21 | 中国科学院半导体研究所 | Alumina dielectric film material with high dielectric constant on silicon substrate and preparing method |
| CN104637961A (en) * | 2013-11-13 | 2015-05-20 | 联华电子股份有限公司 | Semiconductor structure and manufacturing method thereof |
| CN110100296A (en) * | 2017-10-18 | 2019-08-06 | 株式会社爱发科 | Ion source and ion implantation apparatus |
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