CN113178477B - HfO2Ferroelectric thin film and method for depositing same - Google Patents
HfO2Ferroelectric thin film and method for depositing same Download PDFInfo
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- CN113178477B CN113178477B CN202110262011.7A CN202110262011A CN113178477B CN 113178477 B CN113178477 B CN 113178477B CN 202110262011 A CN202110262011 A CN 202110262011A CN 113178477 B CN113178477 B CN 113178477B
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- 238000000151 deposition Methods 0.000 title claims abstract description 52
- 238000000034 method Methods 0.000 title claims abstract description 38
- 239000010409 thin film Substances 0.000 title claims abstract description 23
- 239000010408 film Substances 0.000 claims abstract description 66
- 239000002243 precursor Substances 0.000 claims abstract description 47
- 239000007800 oxidant agent Substances 0.000 claims abstract description 43
- 229910052735 hafnium Inorganic materials 0.000 claims abstract description 41
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims abstract description 39
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims abstract description 38
- 230000001590 oxidative effect Effects 0.000 claims abstract description 31
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 25
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 20
- CJNBYAVZURUTKZ-UHFFFAOYSA-N hafnium(IV) oxide Inorganic materials O=[Hf]=O CJNBYAVZURUTKZ-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000000137 annealing Methods 0.000 claims abstract description 14
- 239000004065 semiconductor Substances 0.000 claims abstract description 12
- 229910000449 hafnium oxide Inorganic materials 0.000 claims abstract description 10
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 7
- 229910052688 Gadolinium Inorganic materials 0.000 claims abstract description 4
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 4
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 62
- 239000007789 gas Substances 0.000 claims description 50
- 238000006243 chemical reaction Methods 0.000 claims description 28
- 238000010926 purge Methods 0.000 claims description 28
- 229910000069 nitrogen hydride Inorganic materials 0.000 claims description 24
- 238000000231 atomic layer deposition Methods 0.000 claims description 17
- 230000008021 deposition Effects 0.000 claims description 17
- 239000011261 inert gas Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 abstract description 23
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 17
- 239000001301 oxygen Substances 0.000 abstract description 17
- 230000007547 defect Effects 0.000 abstract description 9
- WIHZLLGSGQNAGK-UHFFFAOYSA-N hafnium(4+);oxygen(2-) Chemical compound [O-2].[O-2].[Hf+4] WIHZLLGSGQNAGK-UHFFFAOYSA-N 0.000 abstract description 7
- 239000000047 product Substances 0.000 description 44
- 230000002000 scavenging effect Effects 0.000 description 24
- 229910052757 nitrogen Inorganic materials 0.000 description 23
- 239000000758 substrate Substances 0.000 description 14
- 230000008569 process Effects 0.000 description 13
- 230000000694 effects Effects 0.000 description 11
- 239000000463 material Substances 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 230000008878 coupling Effects 0.000 description 6
- 238000010168 coupling process Methods 0.000 description 6
- 238000005859 coupling reaction Methods 0.000 description 6
- -1 nitrogen ions Chemical class 0.000 description 6
- 230000005621 ferroelectricity Effects 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 230000010287 polarization Effects 0.000 description 5
- 229910004143 HfON Inorganic materials 0.000 description 4
- 238000011282 treatment Methods 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 229910052451 lead zirconate titanate Inorganic materials 0.000 description 3
- HFGPZNIAWCZYJU-UHFFFAOYSA-N lead zirconate titanate Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ti+4].[Zr+4].[Pb+2] HFGPZNIAWCZYJU-UHFFFAOYSA-N 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 238000007736 thin film deposition technique Methods 0.000 description 3
- JBRZTFJDHDCESZ-UHFFFAOYSA-N AsGa Chemical compound [As]#[Ga] JBRZTFJDHDCESZ-UHFFFAOYSA-N 0.000 description 2
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 2
- 229910000577 Silicon-germanium Inorganic materials 0.000 description 2
- LEVVHYCKPQWKOP-UHFFFAOYSA-N [Si].[Ge] Chemical compound [Si].[Ge] LEVVHYCKPQWKOP-UHFFFAOYSA-N 0.000 description 2
- 229910052454 barium strontium titanate Inorganic materials 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- VBCSQFQVDXIOJL-UHFFFAOYSA-N diethylazanide;hafnium(4+) Chemical compound [Hf+4].CC[N-]CC.CC[N-]CC.CC[N-]CC.CC[N-]CC VBCSQFQVDXIOJL-UHFFFAOYSA-N 0.000 description 2
- ZYLGGWPMIDHSEZ-UHFFFAOYSA-N dimethylazanide;hafnium(4+) Chemical compound [Hf+4].C[N-]C.C[N-]C.C[N-]C.C[N-]C ZYLGGWPMIDHSEZ-UHFFFAOYSA-N 0.000 description 2
- 229910052732 germanium Inorganic materials 0.000 description 2
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 2
- 239000012212 insulator Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- DJXOAIAWZXGNDH-UHFFFAOYSA-N CC1(C=CC=C1)[Hf](COC)C1(C=CC=C1)C Chemical compound CC1(C=CC=C1)[Hf](COC)C1(C=CC=C1)C DJXOAIAWZXGNDH-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- UCRXQUVKDMVBBM-UHFFFAOYSA-N benzyl 2-amino-3-(4-phenylmethoxyphenyl)propanoate Chemical compound C=1C=CC=CC=1COC(=O)C(N)CC(C=C1)=CC=C1OCC1=CC=CC=C1 UCRXQUVKDMVBBM-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- PDPJQWYGJJBYLF-UHFFFAOYSA-J hafnium tetrachloride Chemical compound Cl[Hf](Cl)(Cl)Cl PDPJQWYGJJBYLF-UHFFFAOYSA-J 0.000 description 1
- GTKHNOIDTQESEF-UHFFFAOYSA-N hafnium(4+) propan-2-ol propan-2-olate Chemical compound CC(C)O.CC(C)O[Hf](OC(C)C)(OC(C)C)OC(C)C GTKHNOIDTQESEF-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000004518 low pressure chemical vapour deposition Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 description 1
- 238000001289 rapid thermal chemical vapour deposition Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 230000007704 transition Effects 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L29/00—Semiconductor devices specially adapted for rectifying, amplifying, oscillating or switching and having potential barriers; Capacitors or resistors having potential barriers, e.g. a PN-junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
- H01L29/02—Semiconductor bodies ; Multistep manufacturing processes therefor
- H01L29/12—Semiconductor bodies ; Multistep manufacturing processes therefor characterised by the materials of which they are formed
- H01L29/24—Semiconductor bodies ; Multistep manufacturing processes therefor characterised by the materials of which they are formed including, apart from doping materials or other impurities, only semiconductor materials not provided for in groups H01L29/16, H01L29/18, H01L29/20, H01L29/22
-
- 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
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
- H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
- H01L21/02172—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides
- H01L21/02175—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides characterised by the metal
- H01L21/02181—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides characterised by the metal the material containing hafnium, e.g. HfO2
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- Engineering & Computer Science (AREA)
- Microelectronics & Electronic Packaging (AREA)
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- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Manufacturing & Machinery (AREA)
- Ceramic Engineering (AREA)
- Formation Of Insulating Films (AREA)
Abstract
The invention relates to HfO2A ferroelectric thin film and a method for depositing the same. HfO2The deposition method of the ferroelectric film comprises the following steps: forming a layer of hydroxyl on the surface of a semiconductor carrier; then depositing a nitrogen oxide film of hafnium and nitrogen oxide films of other elements in sequence, or depositing a nitrogen oxide film of other elements and a nitrogen oxide film of hafnium in sequence; depositing a top electrode; annealing; the hafnium-containing oxynitride film is generated by reacting a hafnium precursor, NH3 and an oxidant; the oxynitride thin film of the other element is formed by reacting a precursor of the other element with NH3 and an oxidizing agent, and the other element is at least one selected from Al, Zr, La, Gd and Si. The invention can effectively reduce the oxygen vacancy defect in the hafnium oxide-based ferroelectric film, thereby improving the reliability of the film.
Description
Technical Field
The invention relates to the field of semiconductor production processes, in particular to HfO2A ferroelectric thin film and a method for depositing the same.
Background
HfO2The base ferroelectric material is a novel ferroelectric material, has excellent ferroelectricity, is compatible with a CMOS (complementary metal oxide semiconductor) process compared with the traditional ferroelectric materials such as PZT (lead zirconate titanate) and BST (barium strontium titanate), and has higher dielectric constant which can control the thickness of a film to be very thin; the ferroelectric material still has stable ferroelectricity under the ultrathin thickness of less than 10nm, and the ferroelectric materials such as PZT, SBT and the like can keep the ferroelectricity when being thicker, so that the sizes of devices such as FeFET and the like can be effectively reduced, and the integration level of a chip is improved; does not contain Pb element, can reduce the pollution to the environment. The growth method of the hafnium oxide based ferroelectric film has a plurality of growth methods, wherein the Atomic Layer Deposition (ALD) method can accurately control the thickness and the components of the film, and the three-dimensional step coverage is more uniform, so that the method is suitable for the development of the future three-dimensional devices.
Despite HfO2The ferroelectric material has excellent ferroelectricity, but due to the existence of defects such as oxygen vacancy, the wake-up effect (the remanent polarization is gradually increased along with the increase of the polarization reversal frequency of the ferroelectric material) caused by the redistribution of the oxygen vacancy in the initial limited cycle frequency, and the transition spike caused by the defects such as oxygen vacancy and the like along with the increase of the cycle frequencyThe fatigue effect caused by the domain wall (the remanent polarization is gradually reduced with the increase of the polarization reversal times of the ferroelectric material) and the poor retention characteristics caused by the charge trapping in the ferroelectric layer counteracting the polarization effect in the ferroelectric layer, which hinder the commercial application thereof. Existing improved HfO2There are many schemes for the reliability of ferroelectric materials, such as electrode replacement, plasma interface treatment, special annealing process treatment, etc. However, the incompatibility of some electrodes and the CMOS process results in inflexible application, inability of plasma interface treatment to effectively passivate defects inside the thin film, and higher cost of the special annealing process. Therefore, these solutions have limitations in the fabrication of large scale integrated circuits.
The invention is therefore set forth.
Disclosure of Invention
The invention mainly aims to provide HfO2The deposition method of the hafnium oxide based ferroelectric film can effectively reduce oxygen vacancy defects in the hafnium oxide based ferroelectric film, thereby improving the reliability thereof.
In order to achieve the above object, the present invention provides the following technical solutions.
HfO2The deposition method of the ferroelectric film comprises the following steps:
forming a layer of hydroxyl on the surface of a semiconductor carrier;
then depositing a nitrogen oxide film of hafnium and nitrogen oxide films of other elements in sequence, or depositing a nitrogen oxide film of other elements and a nitrogen oxide film of hafnium in sequence;
depositing a top electrode;
annealing;
the hafnium-containing oxynitride film is generated by reacting a hafnium precursor, NH3 and an oxidant;
the oxynitride thin film of the other element is formed by reacting a precursor of the other element with NH3 and an oxidizing agent, and the other element is at least one selected from Al, Zr, La, Gd and Si.
Compared with the prior art, the invention achieves the following technical effects.
(1) The invention dopes nitrogen and HfO2The oxygen vacancy coupling in the base ferroelectric film eliminates the capture of electrons by the base ferroelectric film, effectively reduces the oxygen vacancy defect in the hafnium oxide base ferroelectric film, and thus improves the reliability of the hafnium oxide base ferroelectric film.
(2) Meanwhile, the process of the invention is compatible with the traditional CMOS process, has simple process and lower cost, and can be applied to large-scale production.
(3) The method overcomes the defects of complex process, higher cost, inflexible application and the like of other methods, can directly improve the reliability of the film in the growth process of the film, and does not need to add steps after the film is formed.
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.
FIG. 1 is a flow chart of a ferroelectric thin film deposition method provided in example 1 of the present invention;
FIG. 2 is a schematic representation of an embodiment of the present invention with nitrogen ions coupled to oxygen vacancies to eliminate their trapping of electrons;
FIG. 3 is a flow chart of a ferroelectric thin film deposition method provided in embodiment 2 of this invention;
FIG. 4 is a flowchart of a ferroelectric thin film deposition method provided in embodiment 3 of this invention;
fig. 5 is a flowchart of a method for depositing a ferroelectric thin film according to embodiment 4 of the present invention.
Detailed Description
Hereinafter, embodiments of the present disclosure will be described with reference to the accompanying drawings. It should be understood that these descriptions are illustrative only and are not intended to limit the scope of the present disclosure. Moreover, in the following description, descriptions of well-known structures and techniques are omitted so as to not unnecessarily obscure the concepts of the present disclosure.
Various structural schematics according to embodiments of the present disclosure are shown in the figures. The figures are not drawn to scale, wherein certain details are exaggerated and some details may be omitted for clarity of presentation. The shapes of the various regions, layers and their relative sizes, positional relationships are shown in the drawings as examples only, and in practice deviations due to manufacturing tolerances or technical limitations are possible, and a person skilled in the art may additionally design regions/layers with different shapes, sizes, relative positions according to the actual needs.
In the context of the present disclosure, when a layer/element is referred to as being "on" another layer/element, it can be directly on the other layer/element or intervening layers/elements may be present. In addition, if a layer/element is "on" another layer/element in one orientation, then that layer/element may be "under" the other layer/element when the orientation is reversed.
HfO2The ferroelectric film has a series of characteristics such as dielectricity, ferroelectric switch effect, piezoelectric effect, pyroelectric effect, electrooptical effect, acousto-optic effect, photorefractive effect, nonlinear optical effect and the like, as well as bulk materials. The effects can be used independently to manufacture different functional devices, and two or more effects can be used comprehensively to manufacture multifunctional devices, integrated devices or smart devices. However, the reliability is low due to the presence of defects such as oxygen vacancies. Therefore, the invention dopes nitrogen ions in the process of depositing the film, utilizes the doping ions to couple oxygen vacancy coupling, eliminates the capture of electrons, and effectively reduces hafnium oxide (HfO)2) Based on oxygen vacancy defects in the ferroelectric film, thereby improving the reliability of the ferroelectric film, the basic process is as follows:
firstly, forming a layer of hydroxyl on the surface of a semiconductor carrier; the carrier may be any substrate known to those skilled in the art for carrying semiconductor integrated circuit components, such as silicon-on-insulator (SOI), bulk silicon (bulk silicon), germanium, silicon germanium, gallium arsenide, or germanium-on-insulator (ge), and the corresponding top semiconductor material is silicon, germanium, silicon germanium, or gallium arsenide, or may be a carrier having other structures processed on the above-listed substrate, such as a carrier having a structure of a gate, a transistor, or the like. Whenever a certain area of the carrier needs to be deposited with HfO2The ferroelectric thin film is suitable forAre used in the present invention. The hydroxyl group is formed on the surface of the carrier in order to trap the precursor (precursor of hafnium or precursor of another element) on the surface of the carrier.
Then depositing the oxynitride film of hafnium and the oxynitride film of other elements in sequence, or depositing the oxynitride film of other elements and the oxynitride film of hafnium in sequence. The hafnium oxynitride thin film is generated by reacting a hafnium precursor, NH3 and an oxidant. The oxynitride thin film of the other element is formed by reacting a precursor of the other element with NH3 and an oxidizing agent, and the other element is at least one selected from Al, Zr, La, Gd, and Si. The invention is based on the traditional composite HfO2The ferroelectric film is improved on the basis of the ferroelectric film, and the electric characteristics can be obviously improved by compounding the hafnium oxynitride and the non-hafnium oxynitride. The deposition methods used by the two methods include, but are not limited to, LPCVD, ALD, RTCVD or PECVD, and preferably ALD (atomic layer deposition), which is a method for deposition by supplying a reaction gas and a precursor in a pulse manner, i.e., supplying a precursor, an oxidant and ammonia gas in a pulse manner, and the supply order of the oxidant and ammonia gas can be changed.
Taking ALD deposition of the oxynitride film of hafnium as an example, the hafnium precursor, ammonia gas and oxidant are sequentially supplied, or the hafnium precursor, oxidant and ammonia gas are sequentially supplied in each deposition cycle. Among them, hafnium precursors include, but are not limited to, tetrakis (ethylmethylamido) hafnium (TEMAHf), tetrakis (dimethylamido) hafnium (IV) (TDMAHf), tetrakis (diethylamido) hafnium (IV) (TDEAHf), hafnium tetrachloride (HfCl)4) One or more of hafnium isopropoxide-isopropanol adduct, hafnium tert-butoxide, bis (cyclopentadienyl) hafnium dimethyl, bis (trimethylsilyl) amidohafnium (IV) chloride, bis (methyl-cyclopentadienyl) methoxymethylhafnium, or bis (methyl-cyclopentadienyl) hafnium dimethyl. The oxidant can be oxygen, ozone, water, etc.
Purging can be performed after the nitridation reaction or the oxidation reaction is completed to remove impurities such as excessive raw materials or side reaction products, namely, a hafnium precursor, a purging gas, ammonia gas, a purging gas, an oxidant and a purging gas are sequentially supplied in each deposition cycle; or sequentially supplying a hafnium precursor, a purge gas, an oxidizing agent, a purge gas, ammonia gas, and a purge gas. The reaction temperature of the entire deposition cycle is directly related to the precursor and is adjusted accordingly depending on the type.
Taking the ALD deposition of the oxynitride film of the other elements as an example, the precursor, the ammonia gas and the oxidant of the other elements are sequentially supplied in each deposition cycle, or the precursor, the oxidant and the ammonia gas of the other elements are sequentially supplied. Similarly, the oxidant may be oxygen, ozone, water, or the like.
And similarly, adding purging after each reaction is finished, namely sequentially supplying precursors of other elements, purging gas, ammonia gas, purging gas, oxidant and purging gas or sequentially supplying precursors of other elements, purging gas, oxidant, purging gas, ammonia gas and purging gas in each deposition cycle.
When the two films are deposited, the adopted purge gas does not react with reactants, such as inert gas, the number of deposition cycles of the two films is not limited, and the common cycle number is 2-13.
The top electrode is then deposited in order to impart ferroelectricity to the film after annealing, the type of top electrode being not limited, such as the common types of metals.
And finally, annealing under conventional conditions, such as 400-1000 ℃.
The method of the invention does not need to change electrodes, plasma and other treatments after film forming, and special annealing process, and only needs to adopt HfO2The common annealing conditions of the base ferroelectric thin film are sufficient, and thus, the ferroelectric thin film is compatible with the traditional CMOS process.
Preferred embodiments of the present invention are as follows.
Example 1
As shown in fig. 1:
in the first step, a layer of hydroxyl groups is formed on the surface of a semiconductor carrier.
And a second step of forming a hafnium oxynitride thin film by using an ALD method: putting the substrate with the formed layer of hydroxyl into a growth chamber, and introducing a precursor containing Hf to generate a product containing Hf; introducing scavenging gas into the growth chamber, and removing reaction residues of hydroxyl and Hf precursor; introducing NH3 into the growth chamber, and reacting NH3 with the Hf-containing product to generate a Hf-and N-containing product; introducing scavenging gas into the growth chamber to remove reaction residues of NH3 and Hf-containing products; introducing an oxidant into the growth chamber, so that the oxidant reacts with a product containing Hf and N to form a product containing HfON, and simultaneously, forming hydroxyl on the surface of the product; introducing scavenging gas into the growth chamber, and removing residues of the reaction in the previous step; repeating the above steps for multiple times.
Thirdly, forming oxynitride films of other elements by using an ALD method: introducing a precursor containing Al/Zr/La/Gd/Si and other elements into the growth chamber, and reacting hydroxyl with the precursor containing Al/Zr/La/Gd/Si and other elements to form a product containing Al/Zr/La/Gd/Si and other elements; introducing scavenging gas into the growth chamber, and removing residues of the reaction in the previous step; introducing NH3 into the growth chamber, and reacting NH3 with a product containing elements such as Al/Zr/La/Gd/Si to generate a product containing elements such as N and Al/Zr/La/Gd/Si; introducing scavenging gas into the growth chamber, and removing residues of the reaction in the previous step; introducing an oxidant into the growth chamber to enable the oxidant to react with a product containing N and Al/Zr/La/Gd/Si and other elements; introducing scavenging gas into the growth chamber, and removing reaction residues in the previous step; forming a layer of HfO 2-based film containing N, Al/Zr/La/Gd/Si and other elements on the substrate; repeating the steps to form a plurality of HfO 2-based thin films containing N, Al/Zr/La/Gd/Si and other elements on the substrate.
And fourthly, depositing a top electrode.
The fifth step, annealing, during which the nitrogen ions and HfO2The oxygen vacancy coupling in the ferroelectric film eliminates the capture of electrons, and the principle schematic diagram is shown in figure 2.
Example 2
As shown in fig. 3:
in the first step, a layer of hydroxyl groups is formed on the surface of a semiconductor carrier.
And a second step of forming a hafnium oxynitride thin film by using an ALD method: putting the substrate with the formed layer of hydroxyl into a growth chamber, and introducing a precursor containing Hf to generate a product containing Hf; introducing scavenging gas into the growth chamber, and removing reaction residues of hydroxyl and the Hf precursor; introducing an oxidant into the growth chamber, and reacting the oxidant with the Hf-containing product to generate a product containing Hf and O; introducing scavenging gas into the growth chamber, and removing reaction residues of O and products containing Hf; introducing NH3 into the growth chamber, so that NH3 reacts with a product containing Hf and O to form a product containing HfON, and hydroxyl is formed on the surface of the product; introducing scavenging gas into the growth chamber, and removing residues of the reaction in the previous step; repeating the above steps for multiple times.
Thirdly, forming oxynitride films of other elements by using an ALD method: introducing a precursor containing Al/Zr/La/Gd/Si and other elements into the growth chamber, and reacting hydroxyl with the precursor containing Al/Zr/La/Gd/Si and other elements to form a product containing Al/Zr/La/Gd/Si and other elements; introducing scavenging gas into the growth chamber, and removing residues of the reaction in the previous step; introducing an oxidizing agent into the growth chamber, and reacting the oxidizing agent with a product containing elements such as Al/Zr/La/Gd/Si to generate a product containing elements such as N and Al/Zr/La/Gd/Si; introducing scavenging gas into the growth chamber, and removing residues of the reaction in the previous step; introducing NH3 into the growth chamber to react NH3 with products containing O and Al/Zr/La/Gd/Si and other elements; introducing scavenging gas into the growth chamber, and removing reaction residues in the previous step; forming a layer of HfO 2-based film containing N, Al/Zr/La/Gd/Si and other elements on the substrate; repeating the steps to form a plurality of HfO 2-based thin films containing N, Al/Zr/La/Gd/Si and other elements on the substrate.
And fourthly, depositing a top electrode.
The fifth step, annealing, in which the nitrogen ions and HfO2Oxygen vacancy coupling in the ferroelectric film eliminates the capture of electrons.
Example 3
As shown in fig. 4:
in the first step, a layer of hydroxyl groups is formed on the surface of a semiconductor carrier.
And secondly, forming oxynitride films of other elements by using an ALD method: putting the substrate with the formed hydroxyl group into a growth chamber, introducing a precursor containing Al/Zr/La/Gd/Si and other elements into the growth chamber, and reacting the hydroxyl group with the precursor containing Al/Zr/La/Gd/Si and other elements to form a product containing Al/Zr/La/Gd/Si and other elements; introducing scavenging gas into the growth chamber, and removing residues of the reaction in the previous step; introducing NH3 into the growth chamber, and reacting NH3 with a product containing elements such as Al/Zr/La/Gd/Si to generate a product containing elements such as N and Al/Zr/La/Gd/Si; introducing scavenging gas into the growth chamber, and removing residues of the reaction in the previous step; introducing an oxidant into the growth chamber to enable the oxidant to react with a product containing N and Al/Zr/La/Gd/Si and other elements; introducing scavenging gas into the growth chamber, and removing reaction residues in the previous step; forming a layer of HfO 2-based film containing N, Al/Zr/La/Gd/Si and other elements on the substrate; repeating the steps to form a plurality of HfO 2-based thin films containing N, Al/Zr/La/Gd/Si and other elements on the substrate.
Thirdly, forming a hafnium oxynitride film by using an ALD method: introducing a precursor containing Hf to generate a product containing Hf; introducing scavenging gas into the growth chamber, and removing reaction residues of hydroxyl and the Hf precursor; introducing NH3 into the growth chamber, and reacting NH3 with the Hf-containing product to generate a Hf-and N-containing product; introducing scavenging gas into the growth chamber to remove reaction residues of NH3 and Hf-containing products; introducing an oxidant into the growth chamber, reacting the oxidant with a product containing Hf and N to form a product containing HfON, and forming hydroxyl on the surface of the product; introducing scavenging gas into the growth chamber, and removing residues of the reaction in the previous step; repeating the above steps for multiple times.
And fourthly, depositing a top electrode.
The fifth step, annealing, during which the nitrogen ions and HfO2The oxygen vacancy coupling in the ferroelectric film eliminates the capture of electrons.
Example 4
As shown in fig. 5:
in the first step, a layer of hydroxyl groups is formed on the surface of a semiconductor carrier.
And secondly, forming oxynitride films of other elements by using an ALD method: putting the substrate with the hydroxyl group into a growth chamber, introducing a precursor containing Al/Zr/La/Gd/Si and other elements into the growth chamber, and reacting the hydroxyl group with the precursor containing Al/Zr/La/Gd/Si and other elements to form a product containing Al/Zr/La/Gd/Si and other elements; introducing scavenging gas into the growth chamber, and removing residues of the reaction in the previous step; introducing an oxidizing agent into the growth chamber, and reacting the oxidizing agent with a product containing elements such as Al/Zr/La/Gd/Si to generate a product containing elements such as N and Al/Zr/La/Gd/Si; introducing scavenging gas into the growth chamber, and removing residues of the reaction in the previous step; introducing NH3 into the growth chamber to react NH3 with products containing O and Al/Zr/La/Gd/Si and other elements; introducing scavenging gas into the growth chamber, and removing reaction residues in the previous step; forming a layer of HfO 2-based film containing N, Al/Zr/La/Gd/Si and other elements on the substrate; repeating the steps to form a plurality of HfO 2-based thin films containing N, Al/Zr/La/Gd/Si and other elements on the substrate.
Thirdly, forming a hafnium oxynitride film by using an ALD method: introducing a precursor containing Hf to generate a product containing Hf; introducing scavenging gas into the growth chamber, and removing reaction residues of hydroxyl and the Hf precursor; introducing an oxidant into the growth chamber, and reacting the oxidant with the Hf-containing product to generate a product containing Hf and O; introducing scavenging gas into the growth chamber, and removing reaction residues of O and products containing Hf; introducing NH3 into the growth chamber, so that NH3 reacts with a product containing Hf and O to form a product containing HfON, and hydroxyl is formed on the surface of the product; introducing scavenging gas into the growth chamber, and removing residues of the reaction in the previous step; repeating the above steps for multiple times.
And fourthly, depositing a top electrode.
The fifth step, annealing, during which the nitrogen ions and HfO2Oxygen vacancy coupling in the ferroelectric film eliminates the capture of electrons.
The embodiments of the present disclosure are described above. However, these examples are for illustrative purposes only and are not intended to limit the scope of the present disclosure. The scope of the disclosure is defined by the appended claims and equivalents thereof. Various alternatives and modifications can be devised by those skilled in the art without departing from the scope of the present disclosure, and such alternatives and modifications are intended to be within the scope of the present disclosure.
Claims (10)
1. HfO2The method for depositing the ferroelectric thin film is characterized by comprising the following steps:
forming a layer of hydroxyl on the surface of the semiconductor carrier;
then depositing a nitrogen oxide film of hafnium and nitrogen oxide films of other elements in sequence, or depositing a nitrogen oxide film of other elements and a nitrogen oxide film of hafnium in sequence;
depositing a top electrode;
annealing;
wherein the nitrogen oxide film of hafnium consists of a hafnium precursor and NH3And an oxidant are generated through reaction;
the oxynitride film of the other elements consists of precursors of the other elements and NH3And the other element is at least one of Al, Zr, La, Gd and Si.
2. The deposition method according to claim 1, wherein the oxynitride film of hafnium is formed by atomic layer deposition.
3. The deposition method according to claim 1, wherein the oxynitride thin film of the other element is formed by an atomic layer deposition method.
4. The deposition method according to claim 2, wherein the hafnium precursor, the ammonia gas, and the oxidizer are sequentially supplied or the hafnium precursor, the oxidizer, and the ammonia gas are sequentially supplied in each deposition cycle during the deposition of the oxynitride film of hafnium.
5. The deposition method according to claim 4, wherein during the deposition of the oxynitride film of hafnium, a hafnium precursor, a purge gas, ammonia gas, a purge gas, an oxidant, and a purge gas are sequentially supplied for each deposition cycle; or sequentially supplying a hafnium precursor, a purge gas, an oxidizing agent, a purge gas, ammonia gas, and a purge gas.
6. The deposition method according to claim 3, wherein the precursor of the other element, the ammonia gas, and the oxidant are sequentially supplied, or the precursor of the other element, the oxidant, and the ammonia gas are sequentially supplied, in each deposition cycle during the deposition of the oxynitride thin film of the other element.
7. The deposition method according to claim 6, wherein during the deposition of the oxynitride film of hafnium, precursors of other elements, a purge gas, ammonia gas, a purge gas, an oxidant, a purge gas, or precursors of other elements, purge gases, oxidants, purge gases, ammonia gas, purge gases are supplied sequentially in each deposition cycle.
8. The deposition method according to any of claims 1 to 7, wherein the annealing temperature is 400 to 1000 ℃.
9. The deposition method of claim 5 or 7, wherein the purge gas is an inert gas.
10. HfO2A ferroelectric thin film formed by the deposition method according to any one of claims 1 to 9.
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| CN108441830A (en) * | 2018-03-01 | 2018-08-24 | 大连理工大学 | A method of hafnium oxide based ferroelectric film is prepared using reaction magnetocontrol sputtering |
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