CN114959640A - Method for regulating and controlling characteristics of hafnium oxide/zirconium oxide ferroelectric film and application - Google Patents
Method for regulating and controlling characteristics of hafnium oxide/zirconium oxide ferroelectric film and application Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 65
- 229910000449 hafnium oxide Inorganic materials 0.000 title claims abstract description 43
- WIHZLLGSGQNAGK-UHFFFAOYSA-N hafnium(4+);oxygen(2-) Chemical compound [O-2].[O-2].[Hf+4] WIHZLLGSGQNAGK-UHFFFAOYSA-N 0.000 title claims abstract description 43
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 229910001928 zirconium oxide Inorganic materials 0.000 title claims abstract description 41
- 230000001276 controlling effect Effects 0.000 title claims abstract description 15
- 230000001105 regulatory effect Effects 0.000 title claims abstract description 15
- 239000010408 film Substances 0.000 claims description 63
- 238000000151 deposition Methods 0.000 claims description 46
- 238000000231 atomic layer deposition Methods 0.000 claims description 44
- 238000000137 annealing Methods 0.000 claims description 27
- 239000010409 thin film Substances 0.000 claims description 22
- 239000000758 substrate Substances 0.000 claims description 18
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- 230000001590 oxidative effect Effects 0.000 claims description 14
- 239000007800 oxidant agent Substances 0.000 claims description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 12
- 229910052760 oxygen Inorganic materials 0.000 claims description 12
- 239000001301 oxygen Substances 0.000 claims description 12
- 230000008021 deposition Effects 0.000 claims description 11
- 229910052735 hafnium Inorganic materials 0.000 claims description 11
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- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 7
- 230000015654 memory Effects 0.000 claims description 6
- 238000001208 nuclear magnetic resonance pulse sequence Methods 0.000 claims description 4
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 claims description 3
- 230000006698 induction Effects 0.000 claims description 3
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 2
- 239000012159 carrier gas Substances 0.000 claims description 2
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- 230000001143 conditioned effect Effects 0.000 claims 1
- 238000002360 preparation method Methods 0.000 abstract description 5
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- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 21
- 229910052718 tin Inorganic materials 0.000 description 21
- 229910021193 La 2 O 3 Inorganic materials 0.000 description 8
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- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
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Abstract
The invention discloses a method for regulating and controlling the characteristics of a hafnium oxide/zirconium oxide ferroelectric film and application thereof. The invention can well solve the problems that the crystalline phase of the hafnium oxide-based ferroelectric film is difficult to control in the preparation process and the performance is not stable enough because the phase change is easy to occur in the polarization state switching process of the ferroelectric film. The regulating method has stable process and can well meet the high-performance requirement of ferroelectric serving as a storage unit.
Description
Technical Field
The invention belongs to the technical field of semiconductors, and particularly relates to the technical field of ferroelectric thin films, in particular to a method for regulating and controlling the characteristics of a hafnium oxide/zirconium oxide ferroelectric thin film and application thereof.
Background
In recent years, nonvolatile storageThe device is concerned and developed in more and more fields such as artificial intelligence, internet of things, edge computing and the like. Among the many non-volatile memories, hafnium oxide based memories, and particularly hafnium oxide/zirconium oxide based memories, have better CMOS process compatibility and 3D integration capability than other memories, making them of great interest in both academia and industry. The conventional hafnium oxide/zirconium oxide (HZO) ferroelectric thin film has wake-up (wake-up) and fatigue (failure) effects, i.e., the remanent polarization value (Pr) of the thin film is increased and then decreased with the switching times when the thin film is switched. In addition, the durability (endplay) of pure hafnium oxide/zirconium oxide ferroelectric thin films is not particularly high, and thus, in order to improve the durability of the thin films, it is necessary to dope the thin films in an appropriate amount. In the current doping means, the doping of La is proved to be capable of effectively improving the endurance performance of the film, but the amount of La is difficult to control, the doping concentration window is small, the repeatability is poor, and the introduction of more than 1% of La can cause the film to have an uncontrollable and unstable antiferroelectric phenomenon and a strong awakening effect. In conventional doping approaches, one-hundredth mole percent of La doped hafnium oxide/zirconium oxide ferroelectric thin films require ferroelectric thin films to experience as high as 10 a 6 The remanent polarization value can be stabilized after the secondary switch.
The fundamental reason for the above dilemma is that the existing doping techniques do not provide good control of the crystal structure of the hafnium oxide/zirconium oxide crystals by the doping atoms. The ferroelectric phase of the system film belongs to an orthorhombic phase (o-phase), but a monoclinic phase (m-phase), a cubic phase (c-phase) and a tetragonal phase (t-phase) which induces the antiferroelectric property of the film can also appear in the film. There is no systematic method for inducing specific phases to appear in the film when doping hafnium oxide/zirconium oxide. This has put the doping studies on hafnium oxide/zirconium oxide into bottlenecks. A systematic doping method is needed to stabilize the performance of the hafnium oxide/zirconium oxide ferroelectric thin film.
Disclosure of Invention
Therefore, the technical problems to be solved by the invention are that the existing doping method is difficult to make the hafnium oxide/zirconium oxide ferroelectric film present a stable ferroelectric phase (ferroelectric/antiferroelectric), and the film has large fluctuation of Pr value in continuous switching, poor process repeatability and small doping window. Therefore, the application provides a method for regulating and controlling the characteristics of the hafnium oxide/zirconium oxide ferroelectric film.
The technical solution of the invention is as follows: a method for regulating and controlling the characteristics of a hafnium oxide/zirconium oxide ferroelectric film comprises the steps of depositing a hafnium oxide/zirconium oxide film containing a crystallization guide layer of a required doping element on a substrate according to a certain pulse combination sequence by an atomic layer deposition method, and then depositing a top electrode layer to anneal and induce the film to crystallize.
Further, the pulse combination in the atomic layer deposition method is realized by three basic component units;
the first unit A is to sequentially introduce a hafnium precursor and an oxidant pulse into a growth chamber of the atomic layer deposition system to form a layer of atomic layer-level hafnium oxide HfO 2 ；
The second unit B is to sequentially introduce zirconium precursor and oxidant pulses into a growth chamber of the atomic layer deposition system to form a layer of atomic layer-level zirconium oxide ZrO 2 ；
The third unit C is to sequentially introduce precursor pulse and oxidant pulse of specified doping elements into a growth chamber of the atomic layer deposition system to form a layer of oxide E of the doping elements at the atomic layer level x O y Wherein E is the doped element, and x and y are determined by the valence state of the oxide.
Further, pulse combination in the atomic layer deposition method establishes the following eight combination modes on the basis of three basic composition units, wherein the eight combination modes are respectively as follows: m (1): A-B, first depositing HfO 2 Redepositing ZrO 2 (ii) a M (2): B-A, first depositing ZrO 2 Redepositing HfO 2 (ii) a M (3): A-C, first depositing HfO 2 Redeposit E x O y (ii) a M (4): C-A, depositing E first x O y Redepositing HfO 2 (ii) a M (5): B-C, first depositing ZrO 2 Redeposit E x O y (ii) a M (6): C-B, depositing E first x O y Redepositing ZrO 2 (ii) a M (7): a, depositing HfO 2 (ii) a M (8): b, depositing ZrO 2 。
Further, the pulse combination sequence in the atomic layer deposition method is formed on the basis of eight combination modes, and the deposition sequence composition is expressed as
Wherein j i Is belonged to {1,2,3,4,5,6,7,8}, and corresponds to eight combination modes, X i Corresponding to a single mode M (j) i ) The number of repetitions;
in the formed sequence, the atomic environment of the doping elements plays a role in directional induction for subsequent annealing crystallization; m is the number of repetitions of the sequence and is used to control the thickness of the deposited film.
Further, the pulse combination sequence in the atomic layer deposition method satisfies oxide E of the doped element x O y Is covered with HfO 2 Clamping to form HfO 2 /E x O y /HfO 2 Structures, or by ZrO 2 Clamping to form ZrO 2 /E x O y /ZrO 2 Structures, or by HfO 2 And ZrO 2 Clamping to form HfO 2 /E x O y /ZrO 2 And (5) structure.
Further, the growth chamber of the atomic layer deposition system needs to be controlled to a temperature between 200 ℃ and 300 ℃.
Further, the growth chamber of the atomic layer deposition system is fed with precursor pulses and oxidant pulses, which require the assistance of carrier gases, including but not limited to Ar, N 2 And the like.
Further, the growth chamber of the atomic layer deposition system is fed pulses of an oxidizing agent consisting of oxidizing gas molecules, including but not limited to oxygen, ozone, and plasma oxygen generated in various ways.
Further, the film after depositing the top electrode layer needs annealing treatment, the annealing temperature is at 300-800 ℃, the temperature rising rate is 20-100 ℃/s, the annealing time is 10-600 s, and the temperature falling rate is 10-100 ℃/s, wherein the top electrode includes but is not limited to TiN, W, Ni and the like or the combined electrode thereof.
Further, according to different pulse combination sequences and different annealing temperatures of the deposited film, a doped hafnium oxide/zirconium oxide film with precisely controllable film thickness (usually between 4-30 nm) and doping concentration (the atomic molar ratio occupied by the doping element E is usually between 1-20%) is obtained, and according to the atomic environment of the doping element determined by the pulse sequence, the hafnium oxide/zirconium oxide film is induced to form a specified and stable crystal phase, including an orthorhombic (o-phase), a tetragonal (t-phase), a monoclinic (m-phase) and a cubic (c-phase).
Further, the doped elements include, but are not limited to, La, Gd, Al, Si, Y, Sr, Si, etc.
The invention also provides an application of the hafnium oxide/zirconium oxide ferroelectric film regulated and controlled by the method in a memory unit.
The invention has the beneficial effects that:
1. the invention provides a method for regulating and controlling the characteristics of a hafnium oxide/zirconium oxide ferroelectric film, which can freely realize the precise control of the thickness, the type of a doping element and the doping concentration of the film according to the requirements.
2. The pulse sequence during atomic layer deposition is precisely controlled, so that the film can be induced to crystallize towards an orthorhombic phase (o-phase), the ferroelectricity of the film is enhanced, and meanwhile, the doping window is large, and the good process stability is achieved.
3. The ferroelectric film prepared by the invention has a large remanent polarization value, has no awakening and fatigue effects, and has greatly improved durability.
4. The method of the invention can also be used for the production of stable antiferroelectric films (t-phase) or films of other crystalline phases (m-phase, c-phase).
Drawings
Fig. 1 is a schematic structural diagram (a) of a hafnium oxide/zirconium oxide ferroelectric thin film capacitor prepared by atomic layer doping according to the present invention and a schematic structural diagram (b) of a ferroelectric transistor;
FIG. 2 is a schematic diagram of an atomic layer doping pulse combination sequence according to the present invention;
FIG. 3 is a P-V curve of a ferroelectric thin film prepared in accordance with the present invention;
FIG. 4 is a P-V curve of an antiferroelectric film prepared in accordance with the present invention;
FIG. 5 is a TEM analysis of ferroelectric and antiferroelectric thin films prepared according to the present invention;
FIG. 6 is a schematic diagram illustrating the method for controlling the characteristics of the ferroelectric thin film according to the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the following is a detailed description of the operation of the present invention with reference to the accompanying drawings and specific examples. It should be understood that the specific examples described herein are intended only to illustrate the present invention, and are not intended to limit the scope of the invention.
The invention provides a method for regulating and controlling the characteristics of a hafnium oxide/zirconium oxide ferroelectric film, which comprises the steps of depositing a hafnium oxide/zirconium oxide film containing a crystallization guide layer of a required doping element on a substrate according to a certain pulse combination sequence by an atomic layer deposition method, and then depositing a top electrode layer to induce film crystallization by annealing.
Further, the pulse combination in the atomic layer deposition method is realized by three basic constituent units;
the first unit A is to sequentially introduce a hafnium precursor and an oxidant pulse into a growth chamber of the atomic layer deposition system to form a layer of atomic layer-level hafnium oxide HfO 2 ；
The second unit B is to sequentially introduce zirconium precursor and oxidant pulses into a growth chamber of the atomic layer deposition system to form a layer of atomic layer-level zirconium oxide ZrO 2 ；
The third unit C is to sequentially introduce precursor pulse and oxidant pulse of specified doping elements into a growth chamber of the atomic layer deposition system to form a layer of oxide E of the doping elements at the atomic layer level x O y Where E is the element to be doped and x and y are determined by the valence of the oxide.
Further, pulse combinations in the atomic layer deposition method establish the following eight combinations on the basis of three basic constituent unitsModes are respectively as follows: m (1): A-B, first depositing HfO 2 Redepositing ZrO 2 (ii) a M (2): B-A, first depositing ZrO 2 Redepositing HfO 2 (ii) a M (3): A-C, depositing HfO first 2 Redeposit E x O y (ii) a M (4): C-A, depositing E first x O y Redepositing HfO 2 (ii) a M (5): B-C, first depositing ZrO 2 Redeposit E x O y (ii) a M (6): C-B, depositing E first x O y Redepositing ZrO 2 (ii) a M (7): a, depositing HfO 2 (ii) a M (8): b, depositing ZrO 2 。
Further, the pulse combination sequence in the atomic layer deposition method is formed on the basis of eight combination modes, and the deposition sequence composition is expressed as
Wherein j i Is belonged to {1,2,3,4,5,6,7,8}, and corresponds to eight combination modes, X i Corresponding to a single mode M (j) i ) The number of repetitions;
in the formed sequence, the atomic environment of the doping elements plays a role in directional induction for subsequent annealing crystallization; m is the number of repetitions of the sequence and is used to control the thickness of the deposited film.
Further, the pulse combination sequence in the atomic layer deposition method satisfies oxide E of the doped element x O y Is covered with HfO 2 Clamping to form HfO 2 /E x O y /HfO 2 Structures, or by ZrO 2 Clamping to form ZrO 2 /E x O y /ZrO 2 Structures, or by HfO 2 And ZrO 2 Clamping to form HfO 2 /E x O y /ZrO 2 And (5) structure.
According to different pulse combination sequences and different annealing temperatures of the deposited film, the doped hafnium oxide/zirconium oxide film with accurately controllable film thickness and doping concentration is obtained, and the hafnium oxide/zirconium oxide film is induced to form a specified and stable crystalline phase according to the atomic environment of the doping elements determined by the pulse sequence.
Example 1
A method for regulating and controlling the characteristics of a hafnium oxide/zirconium oxide ferroelectric film comprises the following steps:
(1) cleaning of the Si substrate: selection of p + Si<100>Cutting the substrate into square slices of 1cm multiplied by 1cm, and removing impurities on the surface of the Si sheet by using an RCA standard cleaning method;
(2) deposition of TiN bottom electrode: with TiCl 4 And NH 3 As a reactant, TiN with a thickness of about 10nm was deposited at a cavity temperature of 330 ℃ using an atomic layer deposition technique;
(3) preparation of ferroelectric layer film: the sample was placed in the growth chamber of an atomic layer deposition system and the substrate was heated to 280 ℃ using TEMAHf, TEMAZr and La (iprcp) 3 HfO production as precursor sources for hafnium, zirconium and lanthanum, respectively, and plasma oxygen as oxygen source 2 、ZrO 2 And La 2 O 3 (E x O y Specific examples of (d). The order of atomic layer deposition by growth was 2X [ 11X M (1) + 1X M (3) + 12X M (1)]Obtaining a La-doped HZO sample with the atomic molar ratio of Hf, Zr, La of 50 percent, 47 percent and 3 percent and the thickness of about 10nm, wherein the La in the sequence 2 O 3 Is covered with HfO 2 Clamped to form HfO 2 /La 2 O 3 /HfO 2 The structure is beneficial to the film to form o-phase in the annealing process under the La doping concentration and the film thickness;
(4) deposition of TiN/W top electrode: with TiCl 4 And NH 3 Using an atomic layer deposition technology as a reactant, depositing TiN with the thickness of about 10nm at the cavity temperature of 330 ℃, and then continuously depositing a layer of W with the thickness of about 40nm on the TiN by using a physical sputtering method;
(5) annealing treatment: and (3) carrying out rapid annealing treatment at 500 ℃ for 60 seconds on the samples on which all the films are deposited by adopting an RTP (real-time thermal processing) annealing technology.
Example 2
A method for regulating and controlling the characteristics of a hafnium oxide/zirconium oxide ferroelectric film comprises the following steps:
(1) cleaning of the Si substrate: selecting a p + Si <100> substrate, cutting the substrate into square slices of 1cm multiplied by 1cm, and removing impurities on the surface of the Si slice by using an RCA standard cleaning method;
(2) deposition of TiN bottom electrode: with TiCl 4 And NH 3 As a reactant, TiN with a thickness of about 10nm was deposited at a cavity temperature of 330 ℃ using an atomic layer deposition technique;
(3) preparation of ferroelectric layer film: the sample was placed in the growth chamber of an atomic layer deposition system and the substrate was heated to 280 ℃ using TEMAHf, TEMAZr and La (iprcp) 3 HfO production as precursor sources for hafnium, zirconium and lanthanum, respectively, and plasma oxygen as oxygen source 2 、ZrO 2 And La 2 O 3 (E x O y Specific examples of (a) and (b). The order of atomic layer deposition by growth was 8X [ 2X M (2) + 1X M (5) + 3X M (2)]Obtaining La-doped HZO samples with the molar ratio of Hf, Zr and La of 45 percent to 49 percent to 6 percent and the thickness of about 10nm, wherein the La in the sequence 2 O 3 Is ZrO of 2 Clamped to form ZrO 2 /La 2 O 3 /ZrO 2 The structure is beneficial to forming t-phase in the annealing process of the film under the La doping concentration and the film thickness;
(4) deposition of TiN/W top electrode: with TiCl 4 And NH 3 Using an atomic layer deposition technology as a reactant, depositing TiN with the thickness of about 10nm at the cavity temperature of 330 ℃, and then continuously depositing a layer of W with the thickness of about 40nm on the TiN by using a physical sputtering method;
(5) annealing treatment: and (3) carrying out rapid annealing treatment at 500 ℃ for 60 seconds on the samples on which all the films are deposited by adopting an RTP (real-time thermal processing) annealing technology.
A method for regulating and controlling the characteristics of a hafnium oxide/zirconium oxide ferroelectric film comprises the following steps:
(1) cleaning of the Si substrate: selecting a p + Si <100> substrate, cutting the substrate into square slices of 1cm multiplied by 1cm, and removing impurities on the surface of the Si slice by using an RCA standard cleaning method;
(2) deposition of TiN bottom electrode: with TiCl 4 And NH 3 As a reactant, atomic layer deposition technique is usedDepositing TiN with the thickness of about 10nm at the cavity temperature of 330 ℃;
(3) preparation of ferroelectric layer film: the sample was placed in the growth chamber of an atomic layer deposition system and the substrate was heated to 280 ℃ using TEMAHf, TEMAZr and La (iprcp) 3 HfO production as precursor sources for hafnium, zirconium and lanthanum, respectively, and plasma oxygen as oxygen source 2 、ZrO 2 And La 2 O 3 (E x O y Specific examples of (a) and (b). The order of atomic layer deposition by growth was 4X [ 5X M (1) + 1X M (3) + 6X M (1)]Obtaining a La-doped HZO sample with the atomic molar ratio Hf, Zr and La of 49 percent, 45 percent and 6 percent and the thickness of about 10nm, wherein the La in the sequence 2 O 3 Is covered with HfO 2 Clamped to form HfO 2 /La 2 O 3 /HfO 2 The structure is beneficial to the film to form o-phase in the annealing process under the La doping concentration and the film thickness;
(4) deposition of TiN/W top electrode: with TiCl 4 And NH 3 Using an atomic layer deposition technology as a reactant, depositing TiN with the thickness of about 10nm at the cavity temperature of 330 ℃, and then continuously depositing a layer of W with the thickness of about 40nm on the TiN by using a physical sputtering method;
(5) annealing treatment: and (3) carrying out rapid annealing treatment at 500 ℃ for 60 seconds on the samples on which all the films are deposited by adopting an RTP (real-time thermal processing) annealing technology.
Example 4
A method for regulating and controlling the characteristics of a hafnium oxide/zirconium oxide ferroelectric film comprises the following steps:
(1) cleaning of the Si substrate: selecting a p + Si <100> substrate, cutting the substrate into square slices of 1cm multiplied by 1cm, and removing impurities on the surface of the Si slice by using an RCA standard cleaning method;
(2) deposition of TiN bottom electrode: with TiCl 4 And NH 3 As a reactant, TiN with a thickness of about 10nm was deposited at a cavity temperature of 330 ℃ using an atomic layer deposition technique;
(3) preparation of ferroelectric layer film: the sample was placed in the growth chamber of an atomic layer deposition system and the substrate was heated to 280 ℃ using TEMAHf, TEMAZr, and La (iprcp) 3 Are respectively provided withHfO production as precursor source for hafnium, zirconium and lanthanum, and plasma oxygen as oxygen source 2 、ZrO 2 And La 2 O 3 (E x O y Specific examples of (a) and (b). The order of atomic layer deposition by growth was 2X [ 11X M (1) + 1X M (4) + 12X M (2) + 1X M (8)]Obtaining La-doped HZO samples with the molar ratio of Hf, Zr, La of 48.5%: 48.5%: 3% and the thickness of about 10nm, wherein the La is 2 O 3 Is covered with HfO 2 And ZrO 2 Clamped to form HfO 2 /La 2 O 3 /ZrO 2 The structure is beneficial to forming a mixed crystal phase with o-phase and t-phase in the annealing process of the film under the La doping concentration and the film thickness, so that the film has the superposition effect of ferroelectric and antiferroelectric.
(4) Deposition of TiN/W top electrode: with TiCl 4 And NH 3 As a reactant, TiN was deposited to a thickness of about 10nm using an atomic layer deposition technique at a cavity temperature of 330 c, and then a layer of W was continuously deposited on the TiN to a thickness of about 40nm using a physical sputtering method.
(5) Annealing treatment: and (3) carrying out rapid annealing treatment at 500 ℃ for 60 seconds on the samples on which all the films are deposited by adopting an RTP (real-time thermal processing) annealing technology.
Fig. 1 shows the structure of the hafnium oxide/zirconium oxide ferroelectric thin film capacitor prepared by atomic layer doping according to the present invention and the structure of the ferroelectric transistor. Figure 2 shows an atomic layer doping pulse combination sequence.
Comparing example 1 and example 2, and combining the P-V curve tests of fig. 3 and fig. 4, we can clearly find that by using different sequence combinations, the La doped hafnium oxide/zirconium oxide (HZO) thin film can be well controlled to exhibit ferroelectric or antiferroelectric properties. In conjunction with the TEM results of fig. 5, it can be seen that we are well inducing the film to form specific crystalline phases by manipulating the position of the doping element. Fig. 6 illustrates the regulation principle of the present invention.
The foregoing is merely a preferred embodiment of the present invention, and although the present invention has been disclosed in the context of preferred embodiments, it is not intended to be limited thereto. Those skilled in the art can make numerous possible variations and modifications to the present teachings, or modify equivalent embodiments to equivalent variations, without departing from the scope of the present teachings, using the methods and techniques disclosed above. Therefore, any simple modification, equivalent change and modification made to the above embodiments according to the technical essence of the present invention are still within the scope of the protection of the technical solution of the present invention, unless the contents of the technical solution of the present invention are departed.
Claims (10)
1. A method for regulating and controlling the characteristics of a hafnium oxide/zirconium oxide ferroelectric film is characterized in that the hafnium oxide/zirconium oxide film containing a crystallization guide layer of required doping elements is deposited on a substrate according to a certain pulse combination sequence by an atomic layer deposition method, and then a top electrode layer is deposited to induce the crystallization of the film by annealing.
2. The method of claim 1, wherein the pulse combination in the atomic layer deposition method is implemented by three basic units;
the first unit A is to sequentially introduce a hafnium precursor and an oxidant pulse into a growth chamber of the atomic layer deposition system to form a layer of atomic layer-level hafnium oxide HfO 2 ；
The second unit B is to sequentially introduce zirconium precursor and oxidant pulses into a growth chamber of the atomic layer deposition system to form a layer of atomic layer-level zirconium oxide ZrO 2 ；
The third unit C is to sequentially introduce precursor pulse and oxidant pulse of specified doping elements into a growth chamber of the atomic layer deposition system to form a layer of oxide E of the doping elements at the atomic layer level x O y Where E is the element to be doped and x and y are determined by the valence of the oxide.
3. The method for controlling the characteristics of the hafnium oxide/zirconium oxide ferroelectric thin film according to claim 2, wherein the pulse combination in the atomic layer deposition method is implemented by establishing eight combination dies based on three basic composition unitsThe formula is respectively as follows: m (1): A-B, depositing HfO first 2 Redepositing ZrO 2 (ii) a M (2): B-A, first depositing ZrO 2 Redepositing HfO 2 (ii) a M (3): A-C, first depositing HfO 2 Redeposit E x O y (ii) a M (4): C-A, depositing E first x O y Redepositing HfO 2 (ii) a M (5): B-C, first depositing ZrO 2 Redeposition of E x O y (ii) a M (6): C-B, depositing E first x O y Redepositing ZrO 2 (ii) a M (7): a, depositing HfO 2 (ii) a M (8): b, depositing ZrO 2 。
4. The method according to claim 3, wherein the pulse combination sequence of the atomic layer deposition method is configured based on eight combination patterns, and the deposition sequence composition is expressed as
Wherein j i Is belonged to {1,2,3,4,5,6,7,8}, and corresponds to eight combination modes, X i Corresponding to a single mode M (j) i ) The number of repetitions;
in the formed sequence, the atomic environment of the doping elements plays a role in directional induction for subsequent annealing crystallization; m is the number of repetitions of the sequence and is used to control the thickness of the deposited film.
5. The method of claim 4, wherein the sequence of pulse combinations in the ALD method satisfies the oxide E of the doped element x O y Is covered with HfO 2 Clamping to form HfO 2 /E x O y /HfO 2 Structures, or by ZrO 2 Clamping to form ZrO 2 /E x O y /ZrO 2 Structures, or by HfO 2 And ZrO 2 Clamping to form HfO 2 /E x O y /ZrO 2 And (5) structure.
6. The method of claim 2, wherein the temperature of the growth chamber of the ald system is controlled between 200 ℃ and 300 ℃, and the introduction of the precursor pulse and the oxidant pulse requires the use of a carrier gas comprising Ar and N 2 The oxidant pulse is formed by oxidizing gas molecules, including oxygen, ozone, and plasma oxygen.
7. The method as claimed in claim 1, wherein the hafnium oxide/zirconium oxide ferroelectric film is annealed at 800 ℃ and 300 ℃ for 10-600 s at a temperature increase rate of 20-100 ℃/s and a temperature decrease rate of 10-100 ℃/s.
8. The method of claim 1, wherein the doped hafnium oxide/zirconium oxide thin film with precisely controllable thickness and doping concentration is obtained according to different pulse combination sequences and different annealing temperatures of the deposited thin film, and the hafnium oxide/zirconium oxide thin film is induced to form a specific and stable crystalline phase including orthorhombic, tetragonal, monoclinic and cubic phases according to the atomic environment of the doping element determined by the pulse sequence.
9. The method of claim 1, wherein the doped elements include La, Gd, Al, Si, Y, Sr, and Si.
10. Use of the hafnium oxide/zirconium oxide ferroelectric thin film conditioned according to the method of any one of claims 1 to 9 in a memory cell.
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