CN114959640B - Method for regulating and controlling characteristics of hafnium oxide/zirconium oxide ferroelectric film and application thereof - Google Patents
Method for regulating and controlling characteristics of hafnium oxide/zirconium oxide ferroelectric film and application thereof Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 86
- 229910000449 hafnium oxide Inorganic materials 0.000 title claims abstract description 41
- WIHZLLGSGQNAGK-UHFFFAOYSA-N hafnium(4+);oxygen(2-) Chemical compound [O-2].[O-2].[Hf+4] WIHZLLGSGQNAGK-UHFFFAOYSA-N 0.000 title claims abstract description 41
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 229910001928 zirconium oxide Inorganic materials 0.000 title claims abstract description 37
- 230000001276 controlling effect Effects 0.000 title claims abstract description 16
- 230000001105 regulatory effect Effects 0.000 title claims abstract description 16
- 230000015654 memory Effects 0.000 claims abstract description 8
- 239000010408 film Substances 0.000 claims description 69
- 238000000231 atomic layer deposition Methods 0.000 claims description 45
- 238000000137 annealing Methods 0.000 claims description 31
- 238000000151 deposition Methods 0.000 claims description 30
- 239000002243 precursor Substances 0.000 claims description 15
- 239000000758 substrate Substances 0.000 claims description 15
- 239000010409 thin film Substances 0.000 claims description 15
- 239000007800 oxidant agent Substances 0.000 claims description 13
- 230000008021 deposition Effects 0.000 claims description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 11
- 230000001590 oxidative effect Effects 0.000 claims description 11
- 229910052760 oxygen Inorganic materials 0.000 claims description 11
- 239000001301 oxygen Substances 0.000 claims description 11
- 238000002425 crystallisation Methods 0.000 claims description 9
- 230000008025 crystallization Effects 0.000 claims description 9
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 7
- 229910052735 hafnium Inorganic materials 0.000 claims description 7
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 7
- 229910052726 zirconium Inorganic materials 0.000 claims description 7
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 6
- 239000000470 constituent Substances 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
- 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
- 238000001816 cooling Methods 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000013078 crystal Substances 0.000 abstract description 5
- 238000002360 preparation method Methods 0.000 abstract description 5
- 230000010287 polarization Effects 0.000 abstract description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 20
- 238000004140 cleaning Methods 0.000 description 8
- 239000000376 reactant Substances 0.000 description 8
- 229910052746 lanthanum Inorganic materials 0.000 description 6
- 238000010586 diagram Methods 0.000 description 5
- 229910021193 La 2 O 3 Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000002349 favourable effect Effects 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000004544 sputter deposition Methods 0.000 description 4
- 230000027311 M phase Effects 0.000 description 3
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- 239000003990 capacitor Substances 0.000 description 2
- 230000009897 systematic effect Effects 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 238000013473 artificial intelligence Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 230000005621 ferroelectricity Effects 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
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- C23C16/45523—Pulsed gas flow or change of composition over time
- C23C16/45525—Atomic layer deposition [ALD]
- C23C16/45527—Atomic layer deposition [ALD] characterized by the ALD cycle, e.g. different flows or temperatures during half-reactions, unusual pulsing sequence, use of precursor mixtures or auxiliary reactants or activations
- C23C16/45529—Atomic layer deposition [ALD] characterized by the ALD cycle, e.g. different flows or temperatures during half-reactions, unusual pulsing sequence, use of precursor mixtures or auxiliary reactants or activations specially adapted for making a layer stack of alternating different compositions or gradient compositions
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- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/40—Oxides
- C23C16/405—Oxides of refractory metals or yttrium
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/56—After-treatment
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L28/00—Passive two-terminal components without a potential-jump or surface barrier for integrated circuits; Details thereof; Multistep manufacturing processes therefor
- H01L28/40—Capacitors
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L29/00—Semiconductor devices adapted for rectifying, amplifying, oscillating or switching, or capacitors or resistors with at least one potential-jump barrier or surface barrier, e.g. PN junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
- H01L29/40—Electrodes ; Multistep manufacturing processes therefor
- H01L29/43—Electrodes ; Multistep manufacturing processes therefor characterised by the materials of which they are formed
- H01L29/49—Metal-insulator-semiconductor electrodes, e.g. gates of MOSFET
- H01L29/51—Insulating materials associated therewith
- H01L29/516—Insulating materials associated therewith with at least one ferroelectric layer
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L29/00—Semiconductor devices adapted for rectifying, amplifying, oscillating or switching, or capacitors or resistors with at least one potential-jump barrier or surface barrier, e.g. PN junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
- H01L29/66—Types of semiconductor device ; Multistep manufacturing processes therefor
- H01L29/68—Types of semiconductor device ; Multistep manufacturing processes therefor controllable by only the electric current supplied, or only the electric potential applied, to an electrode which does not carry the current to be rectified, amplified or switched
- H01L29/76—Unipolar devices, e.g. field effect transistors
- H01L29/772—Field effect transistors
- H01L29/78—Field effect transistors with field effect produced by an insulated gate
- H01L29/78391—Field effect transistors with field effect produced by an insulated gate the gate comprising a layer which is used for its ferroelectric properties
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 of unstable performance caused by poor control of crystal phase and easy phase change in the polarization state switching process of the ferroelectric film in the preparation process of the hafnium oxide-based ferroelectric film. The regulating method has stable process and can well meet the high performance requirement of ferroelectric serving as a memory cell.
Description
Technical Field
The invention belongs to the technical field of semiconductors, and particularly relates to the technical field of ferroelectric thin film materials, in particular to a method for regulating and controlling characteristics of a hafnium oxide/zirconium oxide ferroelectric thin film and application thereof.
Background
In recent years, nonvolatile memories have been attracting attention and developing in more and more fields such as artificial intelligence, internet of things, and edge computing. Among the numerous non-volatile memories, hafnium oxide-based memories, particularly hafnium oxide/zirconium oxide-based memories, have a better CMOS process compatibility and 3D integration capability than other memories, making them of great interest in both academia and industry. Whereas conventional hafnium oxide/zirconium oxide (HZO) ferroelectric thin films have wake-up and fatigue effects, i.e., when they are switched, the remnant polarization value (Pr) of the thin film is decreased after increasing the number of switching times. In addition, the durability (durability) of the pure hafnium oxide/zirconium oxide ferroelectric film is not particularly high, so that an appropriate amount of doping of the film is required in order to improve the durability of the film. In the current doping means, la doping proves to be capable of effectively improving the endance performance of the film, but the La amount is difficult to control, the doping concentration window is small, the repeatability is poor, and the introduction of more than 1% La can cause uncontrollable and unstable antiferroelectric phenomena and strong wake-up effects of the film. In the conventional doping means, one percent mole ratio of La doped oxideHafnium/zirconium oxide ferroelectric films require ferroelectric films to undergo up to 10 a 6 The residual polarization value can reach stability after the secondary switch.
The root cause of the above-mentioned dilemma is that the existing doping techniques do not achieve good control of the crystal structure of the doping atoms upon crystallization of hafnium oxide/zirconium oxide. The ferroelectric phase of the film belongs to the orthogonal phase (o-phase), but monoclinic phase (m-phase), cubic phase (c-phase) and tetragonal phase (t-phase) which induces the antiferroelectric property of the film also appear in the film. There is no systematic method for inducing specific phases in films when doping hafnium oxide/zirconium oxide. This has resulted in a bottleneck in doping studies on hafnium oxide/zirconium oxide. There is a need for a systematic doping approach to stabilize the performance of hafnium oxide/zirconium oxide ferroelectric thin films.
Disclosure of Invention
Therefore, the technical problem to be solved by the invention is that the hafnium oxide/zirconium oxide ferroelectric film is difficult to display stable ferroelectric phase (ferroelectric/antiferroelectric) by the existing doping method, and the film has larger 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 scheme of the invention is as follows: a method for regulating the characteristics of hafnium oxide/zirconium oxide ferroelectric film includes such steps as depositing hafnium oxide/zirconium oxide film containing the crystal guide layer of needed doping element on substrate by atomic layer deposition, and annealing to induce crystallization.
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 oxidizer pulse into a growth chamber of an atomic layer deposition system to form a layer of atomic layer-level hafnium oxide HfO 2 ；
The second unit B is to sequentially introduce a zirconium precursor and an oxidant pulse into a growth chamber of an atomic layer deposition system to form a layer of atomic layer-level zirconia ZrO 2 ；
The third unit C is to sequentially introduce precursor pulse and oxidant pulse of appointed doping element into the growth chamber of the atomic layer deposition system to form a layer of oxide E of the doping element at the atomic layer level x O y Wherein E is a doped element and x, 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 constituent units, which are respectively: m (1): a-B, first deposit HfO 2 Redeposit ZrO 2 The method comprises the steps of carrying out a first treatment on the surface of the M (2): B-A, depositing ZrO first 2 Redeposition HfO 2 The method comprises the steps of carrying out a first treatment on the surface of the M (3): A-C, first deposit HfO 2 Redeposition E x O y The method comprises the steps of carrying out a first treatment on the surface of the M (4): C-A, first depositing E x O y Redeposition HfO 2 The method comprises the steps of carrying out a first treatment on the surface of the M (5): B-C, first depositing ZrO 2 Redeposition E x O y The method comprises the steps of carrying out a first treatment on the surface of the M (6): C-B, first deposit E x O y Redeposit ZrO 2 The method comprises the steps of carrying out a first treatment on the surface of the M (7): a, depositing HfO 2 The method comprises the steps of carrying out a first treatment on the surface of the 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 is i E {1,2,3,4,5,6,7,8}, corresponding to eight combination patterns, X i Corresponding to a single pattern M (j) i ) The number of repetitions; />
In the formed sequence, the atomic environment of the doping element plays a role in directional induction for the subsequent annealing crystallization; m is the number of repetitions of this sequence, used to control the thickness of the deposited film.
Further, the pulse combination sequence in the atomic layer deposition method satisfies the oxide E of the doped element x O y Is HfO 2 Clamping to form HfO 2 /E x O y /HfO 2 The structure being either ZrO 2 Clamping to form ZrO 2 /E x O y /ZrO 2 Structure or by HfO 2 And ZrO(s) 2 Clamping to form HfO 2 /E x O y /ZrO 2 Structure is as follows.
Further, the growth chamber of the atomic layer deposition system requires temperature control between 200 ℃ and 300 ℃.
Further, the growth chamber of the atomic layer deposition system is fed with the precursor pulse and the oxidizer pulse, with the aid of a carrier gas, including but not limited to Ar, N 2 And inert gases.
Further, the pulses of oxidizer introduced into the growth chamber of the atomic layer deposition system are comprised of oxidizing gas molecules, including, but not limited to, oxygen gas, ozone, and plasma oxygen generated in various ways.
Further, the thin film deposited with the top electrode layer needs annealing treatment, the annealing temperature is 300-800 ℃, the heating rate is 20-100 ℃/s, the annealing time is 10-600 s, the cooling rate is 10-100 ℃/s, wherein the top electrode comprises but is not limited to TiN, W, ni and the like or a combination 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 the film thickness (usually between 4 and 30 nm) and the doping concentration (the atomic mole ratio occupied by the doping element E is usually between 1 and 20%) capable of being precisely controlled is obtained, and according to the atomic environment where the doping element is located, which is determined by the pulse sequence, the hafnium oxide/zirconium oxide film is induced to form a designated and stable crystalline phase, including orthogonal (o-phase), tetragonal (t-phase), monoclinic (m-phase) and cubic (c-phase).
Further, the doped elements include, but are not limited to La, gd, al, si, Y, sr, si and the like.
The invention also provides an application of the hafnium oxide/zirconium oxide ferroelectric film regulated and controlled according to 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 accurate control of the thickness, doping element type and doping concentration of the film according to the requirement.
2. By precisely controlling the pulse sequence during atomic layer deposition, the film can be induced to crystallize towards an orthogonal phase (o-phase), so that the ferroelectricity of the film is enhanced, the doping window is large, and the process stability is good.
3. The ferroelectric film prepared by the invention has larger remnant polarization value, no wake-up and fatigue effects, and greatly improved durability.
4. The method of the invention can also be used for preparing stable antiferroelectric film (t-phase) or film of other crystal phase (m-phase, c-phase).
Drawings
FIG. 1 is a schematic diagram of a structure of a hafnium oxide/zirconium oxide ferroelectric thin film capacitor doped by an atomic layer and a schematic diagram of a ferroelectric transistor (b) prepared by the present invention;
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 according to the present invention;
FIG. 4 is a P-V curve of an antiferroelectric film prepared according to the present invention;
FIG. 5 is a TEM analysis diagram of ferroelectric and antiferroelectric films prepared according to the present invention;
FIG. 6 is a schematic diagram of a method for controlling characteristics of ferroelectric thin films according to the present invention.
Detailed Description
The objects, technical solutions and advantages of the present invention will become more apparent by the following detailed description of the operation of the present invention with reference to the accompanying drawings and specific examples. It should be noted that the specific examples described herein are for illustrative purposes only and are illustrated by way of schematic illustration and are not intended to limit the scope of the present 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 sequentially 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 for annealing to induce film crystallization.
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 oxidizer pulse into a growth chamber of an atomic layer deposition system to form a layer of atomic layer-level hafnium oxide HfO 2 ；
The second unit B is to sequentially introduce a zirconium precursor and an oxidant pulse into a growth chamber of an atomic layer deposition system to form a layer of atomic layer-level zirconia ZrO 2 ；
The third unit C is to sequentially introduce precursor pulse and oxidant pulse of appointed doping element into the growth chamber of the atomic layer deposition system to form a layer of oxide E of the doping element at the atomic layer level x O y Wherein E is a doped element and x, 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 constituent units, respectively: m (1): a-B, first deposit HfO 2 Redeposit ZrO 2 The method comprises the steps of carrying out a first treatment on the surface of the M (2): B-A, depositing ZrO first 2 Redeposition HfO 2 The method comprises the steps of carrying out a first treatment on the surface of the M (3): A-C, first deposit HfO 2 Redeposition E x O y The method comprises the steps of carrying out a first treatment on the surface of the M (4): C-A, first depositing E x O y Redeposition HfO 2 The method comprises the steps of carrying out a first treatment on the surface of the M (5): B-C, first depositing ZrO 2 Redeposition E x O y The method comprises the steps of carrying out a first treatment on the surface of the M (6): C-B, first deposit E x O y Redeposit ZrO 2 The method comprises the steps of carrying out a first treatment on the surface of the M (7): a, depositing HfO 2 The method comprises the steps of carrying out a first treatment on the surface of the 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 is i E {1,2,3,4,5,6,7,8}, corresponding to eight combination patterns, X i Corresponding to a single pattern M (j) i ) The number of repetitions; />
In the formed sequence, the atomic environment of the doping element plays a role in directional induction for the subsequent annealing crystallization; m is the number of repetitions of this sequence, used to control the thickness of the deposited film.
Further, the pulse combination sequence in the atomic layer deposition method satisfies the oxide E of the doped element x O y Is HfO 2 Clamping to form HfO 2 /E x O y /HfO 2 The structure being either ZrO 2 Clamping to form ZrO 2 /E x O y /ZrO 2 Structure or by HfO 2 And ZrO(s) 2 Clamping to form HfO 2 /E x O y /ZrO 2 Structure is as follows.
According to the invention, the doped hafnium oxide/zirconium oxide film with the film thickness and the doping concentration capable of being accurately controlled is obtained according to different pulse combination sequences and different annealing temperatures of the deposited film, and the hafnium oxide/zirconium oxide film is induced to form a designated and stable crystalline phase according to the atomic environment where the doping elements determined by the pulse sequences are located.
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 Si substrate: selecting p + Si<100>A substrate, cut into square slices of 1cm x 1cm, and cleaned by RCA standard cleaning method to remove impurities on the surface of the Si slice;
(2) Deposition of TiN bottom electrode: by TiCl 4 And NH 3 As a reactant, tiN was deposited to a thickness of about 10nm at a chamber temperature of 330 ℃ using atomic layer deposition techniques;
(3) Preparing a ferroelectric layer film: the sample was placed in a growth chamber of an atomic layer deposition system, and the substrate was heated to 280℃using TEMAHf, TEMAZr and La (iprcp) 3 Preparation of HfO as precursor sources for hafnium, zirconium and lanthanum, respectively, and as oxygen source for plasma oxygen 2 、ZrO 2 And La (La) 2 O 3 (E x O y Specific examples of (a) are as follows). The atomic layer deposition sequence adopted for growth is 2 x [11 x M (1) +1*M (3) +12 x M (1)]A sample of La doped with HZO having an atomic molar ratio of Hf: zr: la of 50% to 47% to 3% and a thickness of about 10nm was obtained, la in this sequence 2 O 3 Is HfO 2 Clamped to form HfO 2 /La 2 O 3 /HfO 2 The structure is favorable for forming o-phase in the annealing process of the film under the La doping concentration and the film thickness;
(4) Deposition of TiN/W top electrode: by TiCl 4 And NH 3 As a reactant, tiN having a thickness of about 10nm was deposited at a chamber temperature of 330 ℃ using an atomic layer deposition technique, and then a layer of W having a thickness of about 40nm was continuously deposited on the TiN by a physical sputtering method;
(5) Annealing: the samples on which all films were deposited were subjected to a rapid annealing treatment at 500 ℃ for 60 seconds using RTP annealing techniques.
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 Si substrate: selecting p+Si <100> substrate, cutting into square slices of 1cm multiplied by 1cm, and removing impurities on the surface of the Si slice by RCA standard cleaning method;
(2) Deposition of TiN bottom electrode: by TiCl 4 And NH 3 As a reactant, tiN was deposited to a thickness of about 10nm at a chamber temperature of 330 ℃ using atomic layer deposition techniques;
(3) Preparing a ferroelectric layer film: the sample was placed in a growth chamber of an atomic layer deposition system, and the substrate was heated to 280℃using TEMAHf, TEMAZr and La (iprcp) 3 Preparation of HfO as precursor sources for hafnium, zirconium and lanthanum, respectively, and as oxygen source for plasma oxygen 2 、ZrO 2 And La (La) 2 O 3 (E x O y Specific examples of (a) are as follows). The atomic layer deposition sequence adopted for growth is 8 x [2*M (2) +1*M (5) +3*M (2)]A sample of La doped with HZO having a molar ratio of Hf: zr: la of 45% to 49% to 6% and a thickness of about 10nm was obtained, la in this sequence 2 O 3 By ZrO 2 Clamped to form ZrO 2 /La 2 O 3 /ZrO 2 The structure of (2) is herein La doping concentration andthe thickness of the film is favorable for forming t-phase in the annealing process of the film;
(4) Deposition of TiN/W top electrode: by TiCl 4 And NH 3 As a reactant, tiN having a thickness of about 10nm was deposited at a chamber temperature of 330 ℃ using an atomic layer deposition technique, and then a layer of W having a thickness of about 40nm was continuously deposited on the TiN by a physical sputtering method;
(5) Annealing: the samples on which all films were deposited were subjected to a rapid annealing treatment at 500 ℃ for 60 seconds using RTP annealing techniques.
Example 3
A method for regulating and controlling the characteristics of a hafnium oxide/zirconium oxide ferroelectric film comprises the following steps:
(1) Cleaning of Si substrate: selecting p+Si <100> substrate, cutting into square slices of 1cm multiplied by 1cm, and removing impurities on the surface of the Si slice by RCA standard cleaning method;
(2) Deposition of TiN bottom electrode: by TiCl 4 And NH 3 As a reactant, tiN was deposited to a thickness of about 10nm at a chamber temperature of 330 ℃ using atomic layer deposition techniques;
(3) Preparing a ferroelectric layer film: the sample was placed in a growth chamber of an atomic layer deposition system, and the substrate was heated to 280℃using TEMAHf, TEMAZr and La (iprcp) 3 Preparation of HfO as precursor sources for hafnium, zirconium and lanthanum, respectively, and as oxygen source for plasma oxygen 2 、ZrO 2 And La (La) 2 O 3 (E x O y Specific examples of (a) are as follows). The atomic layer deposition sequence of the growth is 4 [5*M (1) +1*M (3) +6*M (1)]A sample of La doped with HZO having an atomic molar ratio Hf: zr: la of 49% to 45% to 6% and a thickness of about 10nm was obtained, la in this sequence 2 O 3 Is HfO 2 Clamped to form HfO 2 /La 2 O 3 /HfO 2 The structure is favorable for forming o-phase in the annealing process of the film under the La doping concentration and the film thickness;
(4) Deposition of TiN/W top electrode: by TiCl 4 And NH 3 As a reactant, atomic layer deposition techniques were used to deposit a thickness of about 10nm at a chamber temperature of 330 ℃Then, continuing to deposit a layer of W with a thickness of about 40nm on the TiN by using a physical sputtering method;
(5) Annealing: the samples on which all films were deposited were subjected to a rapid annealing treatment at 500 ℃ for 60 seconds using RTP annealing techniques.
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 Si substrate: selecting p+Si <100> substrate, cutting into square slices of 1cm multiplied by 1cm, and removing impurities on the surface of the Si slice by RCA standard cleaning method;
(2) Deposition of TiN bottom electrode: by TiCl 4 And NH 3 As a reactant, tiN was deposited to a thickness of about 10nm at a chamber temperature of 330 ℃ using atomic layer deposition techniques;
(3) Preparing a ferroelectric layer film: the sample was placed in a growth chamber of an atomic layer deposition system, and the substrate was heated to 280℃using TEMAHf, TEMAZr and La (iprcp) 3 Preparation of HfO as precursor sources for hafnium, zirconium and lanthanum, respectively, and as oxygen source for plasma oxygen 2 、ZrO 2 And La (La) 2 O 3 (E x O y Specific examples of (a) are as follows). The atomic layer deposition sequence adopted for growth is 2 x [11 x M (1) +1*M (4) +12 x M (2) +1*M (8)]A La-doped HZO sample having a molar ratio Hf: zr: la of 48.5% to 3% and a thickness of about 10nm was obtained, la in this sequence 2 O 3 Is HfO 2 And ZrO(s) 2 Clamped to form HfO 2 /La 2 O 3 /ZrO 2 The structure is favorable for forming a mixed crystal phase with both 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: by TiCl 4 And NH 3 As a reactant, tiN was deposited to a thickness of about 10nm at a chamber temperature of 330 ℃ using an atomic layer deposition technique, followed by a continuous deposition of W to a layer thickness of about 40nm on TiN by physical sputtering.
(5) Annealing: the samples on which all films were deposited were subjected to a rapid annealing treatment at 500 ℃ for 60 seconds using RTP annealing techniques.
Fig. 1 shows the structure of a hafnium oxide/zirconium oxide ferroelectric thin film capacitor doped by an atomic layer and the structure of a ferroelectric transistor prepared by the present invention. Fig. 2 shows an atomic layer doping pulse combination sequence.
Comparing examples 1 and 2, and combining the P-V curve tests of fig. 3 and 4, we can clearly find that by using different sequence combinations, la doped hafnium oxide/zirconium oxide (HZO) films can be well controlled to exhibit ferroelectric or antiferroelectric properties. In combination with the TEM results of fig. 5, it can be seen that we induced the film well to form a specific crystalline phase by modulating 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 the present invention has been disclosed in the above description of the preferred embodiment, but is not limited thereto. Any person skilled in the art can make many possible variations and modifications to the technical solution of the present invention or modifications to equivalent embodiments using the methods and technical contents disclosed above, without departing from the scope of the technical solution of the present invention. Therefore, any simple modification, equivalent variation and modification of the above embodiments according to the technical substance of the present invention still fall within the scope of the technical solution of the present invention.
Claims (3)
1. A method for regulating and controlling the characteristics of a hafnium oxide/zirconium oxide ferroelectric film is characterized in that a hafnium oxide/zirconium oxide film containing a crystallization guide layer of a required doping element 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 for annealing to induce film crystallization; wherein the pulse combination in the atomic layer deposition method is realized by three basic constituent units, and the first unit A is to sequentially introduce a hafnium precursor and an oxidant pulse into a growth chamber of an atomic layer deposition system to form a layer of atomic layer-level hafnium oxide HfO 2 The method comprises the steps of carrying out a first treatment on the surface of the The second unit B is sequentially arranged inIntroducing zirconium precursor and oxidant pulse into the growth chamber of atomic layer deposition system to form a layer of atomic layer-level zirconia ZrO 2 The method comprises the steps of carrying out a first treatment on the surface of the The third unit C is to sequentially introduce precursor pulse and oxidant pulse of appointed doping element into the growth chamber of the atomic layer deposition system to form a layer of oxide E of the doping element at the atomic layer level x O y Wherein E is a doped element, x and y are determined by the valence state of the oxide, and the doped element comprises La;
the temperature of the growth chamber of the atomic layer deposition system is controlled between 200 ℃ and 300 ℃, and the precursor pulse and the oxidant pulse are introduced by carrier gas comprising Ar and N 2 The introduced oxidant pulse is composed of oxidative gas molecules, including oxygen, ozone and plasma oxygen;
the film deposited with the top electrode layer needs annealing treatment, the annealing temperature is 300-800 ℃, the heating rate is 20-100 ℃/s, the annealing time is 10-600 s, and the cooling rate is 10-100 ℃/s;
pulse combination in the atomic layer deposition method establishes the following eight combination modes on the basis of three basic constituent units, respectively: m (1): a-B, first deposit HfO 2 Redeposit ZrO 2 The method comprises the steps of carrying out a first treatment on the surface of the M (2): B-A, depositing ZrO first 2 Redeposition HfO 2 The method comprises the steps of carrying out a first treatment on the surface of the M (3): A-C, first deposit HfO 2 Redeposition E x O y The method comprises the steps of carrying out a first treatment on the surface of the M (4): C-A, first depositing E x O y Redeposition HfO 2 The method comprises the steps of carrying out a first treatment on the surface of the M (5): B-C, first depositing ZrO 2 Redeposition E x O y The method comprises the steps of carrying out a first treatment on the surface of the M (6): C-B, first deposit E x O y Redeposit ZrO 2 The method comprises the steps of carrying out a first treatment on the surface of the M (7): a, depositing HfO 2 The method comprises the steps of carrying out a first treatment on the surface of the M (8): b, depositing ZrO 2 The method comprises the steps of carrying out a first treatment on the surface of the 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 is i E {1,2,3,4,5,6,7,8}, corresponding to eight combination patterns, X i Corresponding to a single pattern M (j) i ) The number of repetitions;
in the formed sequence, the atomic environment of the doping element plays a role in directional induction for the subsequent annealing crystallization; m is the repetition number of the sequence and is used for controlling the thickness of the deposited film; the pulse combination sequence in the atomic layer deposition method satisfies the oxide E of the doped element x O y Is HfO 2 Clamping to form HfO 2 /E x O y /HfO 2 The structure being either ZrO 2 Clamping to form ZrO 2 /E x O y /ZrO 2 Structure or by HfO 2 And ZrO(s) 2 Clamping to form HfO 2 /E x O y /ZrO 2 Structure is as follows.
2. The method for controlling the characteristics of a hafnium oxide/zirconium oxide ferroelectric thin film according to claim 1, wherein the hafnium oxide/zirconium oxide doped thin film with precisely controllable film 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 designated and stable crystalline phase including orthogonal, tetragonal, monoclinic and cubic phases according to the atomic environment where the doping element is located, which is determined by the pulse sequence.
3. Use of a hafnium oxide/zirconium oxide ferroelectric thin film as regulated by the method according to any one of claims 1-2 in a memory cell.
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