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WO2021253527A1 - 一种HfO2基铁电电容器及其制备方法和HfO2基铁电存储器 - Google Patents

一种HfO2基铁电电容器及其制备方法和HfO2基铁电存储器 Download PDF

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WO2021253527A1
WO2021253527A1 PCT/CN2020/100984 CN2020100984W WO2021253527A1 WO 2021253527 A1 WO2021253527 A1 WO 2021253527A1 CN 2020100984 W CN2020100984 W CN 2020100984W WO 2021253527 A1 WO2021253527 A1 WO 2021253527A1
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layer
hfo
ferroelectric capacitor
intercalation
based ferroelectric
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French (fr)
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罗庆
姜鹏飞
吕杭炳
王渊
刘明
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Institute of Microelectronics of CAS
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    • H—ELECTRICITY
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    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/004—Details
    • H01G9/04—Electrodes or formation of dielectric layers thereon
    • H01G9/042—Electrodes or formation of dielectric layers thereon characterised by the material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G7/00—Capacitors in which the capacitance is varied by non-mechanical means; Processes of their manufacture
    • H01G7/06—Capacitors in which the capacitance is varied by non-mechanical means; Processes of their manufacture having a dielectric selected for the variation of its permittivity with applied voltage, i.e. ferroelectric capacitors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
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    • H01G4/00—Fixed capacitors; Processes of their manufacture
    • H01G4/002—Details
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    • H01G4/008—Selection of materials
    • H—ELECTRICITY
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    • H—ELECTRICITY
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    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G4/00—Fixed capacitors; Processes of their manufacture
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    • H01G4/018—Dielectrics
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    • H—ELECTRICITY
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    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G4/00—Fixed capacitors; Processes of their manufacture
    • H01G4/33—Thin- or thick-film capacitors (thin- or thick-film circuits; capacitors without a potential-jump or surface barrier specially adapted for integrated circuits, details thereof, multistep manufacturing processes therefor)
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
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    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/004—Details
    • H01G9/04—Electrodes or formation of dielectric layers thereon
    • H01G9/048—Electrodes or formation of dielectric layers thereon characterised by their structure
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
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    • H01G9/07—Dielectric layers
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    • H10B—ELECTRONIC MEMORY DEVICES
    • H10B53/00—Ferroelectric RAM [FeRAM] devices comprising ferroelectric memory capacitors
    • H10B53/30—Ferroelectric RAM [FeRAM] devices comprising ferroelectric memory capacitors characterised by the memory core region
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    • H10D1/696—Electrodes comprising multiple layers, e.g. comprising a barrier layer and a metal layer
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10D—INORGANIC ELECTRIC SEMICONDUCTOR DEVICES
    • H10D1/00—Resistors, capacitors or inductors
    • H10D1/60—Capacitors
    • H10D1/68—Capacitors having no potential barriers
    • H10D1/682—Capacitors having no potential barriers having dielectrics comprising perovskite structures
    • H10D1/684—Capacitors having no potential barriers having dielectrics comprising perovskite structures the dielectrics comprising multiple layers, e.g. comprising buffer layers, seed layers or gradient layers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present application belongs to the technical field of microelectronics, in particular, to a ferroelectric capacitor group HfO 2, preparation method and HfO 2-yl ferroelectric memory.
  • Ferroelectric Random Access Memory is one of the representative new devices.
  • the structure of a ferroelectric memory cell is similar to that of a dynamic random access memory (DRAM), consisting of a field effect transistor (MOSFET) and a ferroelectric capacitor.
  • DRAM dynamic random access memory
  • MOSFET field effect transistor
  • ferroelectric capacitor is the part where information is stored.
  • the dielectric layer is ferroelectric and has a polarization hysteresis curve.
  • the polarization direction of the ferroelectric domain is used to represent the binary "0" and " 1" stores information, and its residual polarization intensity value represents the storage window size of the memory.
  • the polarization reversal time of the ferroelectric domain is on the order of nanoseconds, so the writing speed of the ferroelectric memory is faster and the energy consumption is lower.
  • HfO2-based ferroelectric memory is a new generation of non-volatile semiconductor memory with great development potential.
  • non-centrosymmetric orthogonal phase o-phase, spatial cluster Pca2 1
  • the bulk phase of HfO 2 is a centrally symmetrical monoclinic phase (m phase, spatial cluster P2 1 /c), which does not have ferroelectricity.
  • asymmetrical stress mainly vertical tensile stress and horizontal compressive stress
  • a phase transition from m-phase to o-phase occurs, and the film appears ferroelectric.
  • the component ratio of the o phase determines the strength of the ferroelectricity of the material, which can be directly reflected by the remanent polarization (P r ).
  • Remaining polarization is one of the key parameters of ferroelectric memory.
  • 2P r is regarded as the storage window size of the memory. Increasing the storage window size can effectively prevent misreading of information, thereby improving the reliability of the memory.
  • this application aims to provide a HfO 2 -based ferroelectric capacitor, a preparation method thereof, and a HfO 2 -based ferroelectric memory, so as to achieve the purpose of increasing the storage window of the ferroelectric memory.
  • This application provides a HfO 2 based ferroelectric capacitor, which includes a substrate layer, a lower electrode, a dielectric layer, an Al 2 O 3 intercalation layer, an upper electrode, and a metal protection layer from bottom to top.
  • the material of the substrate layer is SiO 2 /Si or SiO 2 .
  • the lower electrode material is TiN, and the thickness is 10-60 nm.
  • the dielectric layer is HZO
  • the molar composition ratio of Hf and Zr is (0.4-0.6): (0.4-0.6)
  • the thickness is 8-15 nm.
  • the thickness of the Al 2 O 3 intercalation layer is 2 nm to 3 nm.
  • the upper electrode material is TiN, and the thickness is 10-60 nm.
  • This application also provides a method for preparing a HfO 2 -based ferroelectric capacitor, which includes the following steps:
  • coating photoresist on the Al 2 O 3 intercalation layer, exposure and development are: coating negative glue on the Al 2 O 3 intercalation layer, bake 1 min before 150 °C, and bake 1 min after exposure at 120 °C, in the developer solution Soak in the medium for 30s to develop, rinse and blow dry with deionized water.
  • removing the photoresist and excess metal includes the following steps: soaking in an acetone solution until the photoresist and excess metal fall off; soaking in absolute ethanol to remove acetone; and rinsing with deionized water and drying.
  • the present application further provides a HfO 2-yl ferroelectric memory, comprising the ferroelectric capacitor group HfO 2 or HfO 2-yl preparing a ferroelectric capacitor obtained by the above preparation method.
  • an Al 2 O 3 intercalation layer with a thermal expansion coefficient smaller than TiN is inserted between the dielectric layer of the ferroelectric capacitor and the upper electrode (TiN) to provide stronger tensile stress during the annealing process, thereby improving
  • TiN upper electrode
  • the composition ratio of the o-phase in the medium ultimately achieves the purpose of increasing the residual polarization and increasing the storage window of the ferroelectric memory. Increasing the size of the storage window can effectively prevent misreading of information, thereby improving the reliability of the memory.
  • the dielectric layer is HZO (hafnium-zirconium oxide)
  • the molar composition ratio of Hf and Zr is (0.4 ⁇ 0.6): (0.4 ⁇ 0.6)
  • the thickness is 8 ⁇ 15nm. At this time, it has the strongest iron Electrical.
  • Fig. 1 is a schematic diagram of the structure of the HZO ferroelectric capacitor of embodiment 1;
  • FIG. 2 is a comparison diagram of PV characteristics of Example 1.
  • a layer/element when a layer/element is referred to as being “on” another layer/element, the layer/element may be directly on the other layer/element, or there may be an intermediate layer/element between them. element.
  • the layer/element may be located "under” the other layer/element when the orientation is reversed.
  • the present application provides a HfO 2-yl ferroelectric capacitor, comprising in sequence from the lower substrate layer 1 to 2, the lower electrode 3 dielectric layer, Al 2 O 3 layer 4 is inserted, the upper electrode 5 and the metallic protective layer 6 .
  • the material of the substrate layer 1 may be SiO 2 alone, or SiO 2 /Si arranged from top to bottom.
  • the material of the substrate layer 1 is SiO 2 /Si, preferably, the thickness of SiO 2 is 100-500 nm, and the thickness of Si is 300-600 ⁇ m.
  • the materials of the lower electrode 2 and the upper electrode 5 are both TiN.
  • the thickness of TiN is 10 nm-60 nm. If the thickness is less than 10 nm, ferroelectricity may be lost, and material waste if the thickness is greater than 60 nm. Exemplarily, the thickness is 40 nm.
  • the dielectric layer 3 is a HfO 2 based material.
  • the dielectric layer 3 is HZO (hafnium-zirconium oxide), the molar composition ratio of Hf and Zr is (0.4 ⁇ 0.6): (0.4 ⁇ 0.6), and the thickness is 8 ⁇ 15nm, at this time, has the strongest ferroelectricity, exemplary, the thickness is 10nm.
  • the molar composition ratio of Hf and Zr is 1:1, at this time, the ferroelectricity of the dielectric layer 3 is the strongest.
  • the dielectric layer 3 may also be a HfO 2 based material doped with other elements (such as Si, Y, Gd, etc.).
  • the application inserts an Al 2 O 3 intercalation layer with a thermal expansion coefficient smaller than TiN between the dielectric layer of the ferroelectric capacitor and the upper electrode (TiN) to provide stronger tensile stress during the annealing process. It can increase the proportion of o-phase components in the medium, and finally achieve the purpose of increasing the residual polarization and increasing the storage window of the ferroelectric memory. Increasing the size of the storage window can effectively prevent misreading of information, thereby improving the reliability of the memory.
  • the thickness of the Al 2 O 3 intercalation layer 4 is 2 nm to 3 nm. If it is too thin, the effect of stress will not be obvious, and if it is too thick, it will have a greater impact on the electrical characteristics of the device, such as dielectric interference, resistance partial pressure, etc.
  • the material of the metal protection layer 6 is inert metals such as Pd, Au, Pt, etc., with a thickness of 10-30 nm, and exemplarily, 20 nm.
  • this application provides a method for preparing a HfO 2 based ferroelectric capacitor, which includes the following steps:
  • Step 1 cleaning the substrate 1: the substrate is immersed in acetone and absolute ethanol, cleaned, and blow-dried in sequence; then immersed in deionized water, rinsed, and blow-dried.
  • Step 2 On the substrate 1, the lower electrode 2 is prepared by sputtering using an ion beam sputtering process.
  • the sputtering process includes, but is not limited to, ion beam sputtering, direct current sputtering, reactive sputtering, etc.
  • ion beam sputtering process is used: TiN target, beam current voltage 700 ⁇ 900V, beam current 40 ⁇ 60mA, acceleration voltage 150 ⁇ 170V, gas is Ar/N 2 mixed gas, flow rate is (7 ⁇ 9sccm) respectively /(4 ⁇ 6sccm).
  • TiN target beam current voltage 700 ⁇ 900V
  • beam current 40 ⁇ 60mA beam current 40 ⁇ 60mA
  • acceleration voltage 150 ⁇ 170V gas
  • gas Ar/N 2 mixed gas
  • flow rate is (7 ⁇ 9sccm) respectively /(4 ⁇ 6sccm).
  • a better film contrast can be obtained within this process range, which is beneficial to the generation of ferroelectricity.
  • Step 3 deposit a dielectric layer 3 on the bottom electrode 2.
  • an ALD process is used to prepare the HZO dielectric layer.
  • a layer of ZrO 2 is grown first, and then a layer of HfO 2 is grown, and the cycle is repeated, and the last layer of ZrO 2 is capped.
  • the deposition temperature range is usually 280-300°C.
  • the precursors of Zr and Hf are heated to 100-140°C, the deionized water is kept at a room temperature of 20°C, the carrier gas is N 2 , and the gas flow rate is 40-80 sccm.
  • the precursor of Hf adopts tetrakis(ethylmethylamido)hafnium(IV) (Tetrakis(ethylmethylamido)hafnium(IV), TEMAH), the chemical formula Hf(NCH 3 C 2 H 5 ) 4 ; the precursor of Zr Tetrakis (ethylmethylamido) zirconium (IV), TEMAZ) with the chemical formula Zr(NCH 3 CH 5 ) 4 is used; deionized water is used as the oxygen source.
  • Step 4 deposit an Al 2 O 3 intercalation layer 4 on the dielectric layer 3 by using an ALD process.
  • TMA Trimethylaluminum
  • Al(CH 3 ) 3 the chemical formula Al(CH 3 ) 3 as the precursor of Al
  • deionized water the oxygen source
  • the deposition temperature 280-300°C
  • the precursor of Al and deionized water Keep the room temperature at 20°C
  • select N 2 as the carrier gas
  • the gas flow rate is 40-80 sccm.
  • Step 5 apply photoresist, expose and develop.
  • Step 6 using a sputtering process to prepare the upper electrode 5 by sputtering
  • the sputtering process includes, but is not limited to, ion beam sputtering, direct current sputtering, reactive sputtering, etc.
  • ion beam sputtering process is used: TiN target, beam current voltage 700 ⁇ 900V, beam current 40 ⁇ 60mA, acceleration voltage 150 ⁇ 170V, gas is Ar/N 2 mixed gas, flow rate is (7 ⁇ 9sccm) respectively /(4 ⁇ 6sccm).
  • TiN target beam current voltage 700 ⁇ 900V
  • beam current 40 ⁇ 60mA beam current 40 ⁇ 60mA
  • acceleration voltage 150 ⁇ 170V gas
  • gas Ar/N 2 mixed gas
  • flow rate is (7 ⁇ 9sccm) respectively /(4 ⁇ 6sccm).
  • a better film contrast can be obtained within this process range, which is beneficial to the generation of ferroelectricity.
  • Step 7 using a sputtering process to sputter the metal protective layer 6;
  • an ion beam sputtering process is used: Pd target, beam current voltage 700-900V, beam current 40-60mA, acceleration voltage 150-170V, gas is Ar, and flow rate is 7-9 sccm.
  • Step 8 Remove the photoresist and excess metal.
  • Step 801 soaking in an acetone solution until the photoresist and excess metal fall off;
  • Step 802 soaking in absolute ethanol to remove acetone
  • Step 803 rinse and blow dry with deionized water.
  • Step 9 rapid thermal annealing in a N 2 atmosphere at 400-500° C., and the rapid thermal annealing time is less than 1 min, preferably 20-30 s.
  • This application also provides a HfO 2 -based ferroelectric memory, including the above-mentioned HfO 2 -based ferroelectric capacitor.
  • a kind of HfO 2 base ferroelectric capacitor is shown in Fig. 1, from bottom to top, it is the substrate layer SiO 2 /Si1, the lower electrode 2, the dielectric layer 3, the Al 2 O 3 intercalation layer 4, the upper electrode 5, and the metal protective layer. 6.
  • the thickness of the upper layer of SiO 2 is 300 nm, and the thickness of the lower layer of Si is 500 ⁇ m. Then the substrate is soaked and cleaned with acetone and absolute ethanol for 3 minutes, and then blown dry; then soaked and rinsed with deionized water 3min, blow dry, complete the cleaning of the substrate.
  • the TiN bottom electrode, TiN target, beam current voltage 800V, beam current 46mA, accelerating voltage 160V, and Ar/N 2 mixed gas are prepared by sputtering with ion beam sputtering process.
  • the gas flow rate is 8 sccm/5 sccm, and the thickness of the TiN bottom electrode can be 40 nm.
  • an ALD process is used to prepare the HZO dielectric layer, using TEMAH and TEMAZ as the precursors of Hf and Zr, and using deionized water as the oxygen source.
  • the deposition temperature is 280°C
  • the precursors of Zr and Hf are heated to 120°C
  • the deionized water is kept at a room temperature of 20°C
  • the carrier gas is N 2
  • the gas flow rate is 50 sccm.
  • a layer of ZrO 2 is grown first, and then a layer of HfO 2 is grown, and then circulated in turn, and the last layer of ZrO 2 is capped.
  • the deposition rates are (which is Per cycle) (ZrO 2 ), (which is Each cycle) (HfO 2 ), so as to ensure that the stoichiometric ratio of Hf and Zr is approximately equal to 1:1, that is, the composition ratio of Hf and Zr is 1:1.
  • the thickness of the deposition to the dielectric layer is 10 nm to complete the preparation of the dielectric layer.
  • an Al 2 O 3 intercalation layer is prepared by an ALD process, trimethyl aluminum is selected as the precursor of Al, and deionized water is used as the oxygen source.
  • the deposition temperature is 300°C
  • the Al precursor and deionized water are kept at room temperature of 20°C
  • the carrier gas is N 2
  • the gas flow rate is 50sccm
  • the deposition rate is The thickness of the Al 2 O 3 intercalation layer may be 2 nm.
  • a Pd metal protective layer, a Pd target, a beam voltage of 800V, a beam current of 46mA, an acceleration voltage of 160V, a gas of Ar, a flow rate of 8 sccm, and a thickness of the metal protective layer were prepared by sputtering on the formed upper electrode. 20nm.
  • the above operation will be obtained by having a substrate layer, an electrode, a dielectric layer, Al 2 O 3 layer is interposed, the upper electrode, HfO 2 electrical component iron metal protective layer to the photoresist and excess metal immersed in an acetone solution Fall off; then soak in absolute ethanol to remove acetone; then rinse with deionized water and blow dry.
  • HfO 2 -based ferroelectric devices were annealed under N 2 atmosphere and 500° C. for 30 s to obtain HfO 2 -based ferroelectric capacitors.
  • the substrate is cleaned: the substrate is soaked and cleaned with acetone and absolute ethanol for 5 minutes, and then dried; Soak and rinse in ionized water for 5 minutes and blow dry to complete the cleaning of the substrate.
  • the TiN bottom electrode, TiN target, beam current voltage 700V, beam current 40mA, acceleration voltage 150V, and gas mixed with Ar/N 2 are prepared by sputtering using ion beam sputtering process.
  • the gas flow rate is 7 sccm/4 sccm, respectively, and the thickness of the TiN bottom electrode can be 60 nm.
  • the HZO dielectric layer is prepared by the ALD process, using TEMAH and TEMAZ as the precursors of Hf and Zr, and using deionized water as the oxygen source.
  • the deposition temperature is 290°C
  • the precursors of Zr and Hf are heated to 100°C
  • the deionized water is kept at a room temperature of 20°C
  • the carrier gas is N 2
  • the gas flow rate is 60 sccm.
  • a layer of ZrO 2 is grown first, and then a layer of HfO 2 is grown, and the cycle is repeated, and the last layer of ZrO 2 is capped.
  • the composition ratio of Hf and Zr is 0.4:0.6
  • the thickness of the deposited dielectric layer is 10nm to complete the preparation of the dielectric layer.
  • an Al 2 O 3 intercalation layer is prepared by an ALD process, and trimethyl aluminum is selected as the precursor of Al, and deionized water is used as the oxygen source.
  • the deposition temperature is 280°C
  • the Al precursor and deionized water are kept at a room temperature of 20°C
  • the carrier gas is N 2
  • the gas flow rate is 60 sccm
  • the thickness of the Al 2 O 3 intercalation layer can be 3 nm.
  • a Pd metal protective layer a Pd target, a beam current voltage of 700V, a beam current of 40mA, an acceleration voltage of 150V, a gas of Ar, a flow rate of 7 sccm, and a thickness of the metal protective layer 10nm.
  • the above operation will be obtained by having a substrate layer, an electrode, a dielectric layer, Al 2 O 3 layer is interposed, the upper electrode, HfO 2 electrical component iron metal protective layer to the photoresist and excess metal immersed in an acetone solution Fall off; then soak in absolute ethanol to remove acetone; then rinse with deionized water and blow dry.
  • HfO 2 -based ferroelectric devices were annealed under the conditions of N 2 atmosphere and 400° C. for 25 s to obtain HfO 2 -based ferroelectric capacitors.
  • the substrate is cleaned: the substrate is soaked and cleaned with acetone and absolute ethanol for 3 minutes, and then blown dry; Soak and rinse in ionized water for 3 minutes and blow dry to complete the cleaning of the substrate.
  • the TiN bottom electrode, TiN target, beam current voltage 900V, beam current 60mA, accelerating voltage 170V, gas is Ar/N 2 mixed by sputtering prepared by ion beam sputtering process
  • the gas flow rate is 9 sccm/6 sccm, respectively, and the thickness of the TiN bottom electrode can be 20 nm.
  • an ALD process is used to prepare the HZO dielectric layer, using TEMAH and TEMAZ as the precursors of Hf and Zr, and using deionized water as the oxygen source.
  • the deposition temperature is 300°C
  • the precursors of Zr and Hf are heated to 140°C
  • the deionized water is kept at a room temperature of 20°C
  • the carrier gas is N 2
  • the gas flow rate is 70 sccm.
  • a layer of ZrO 2 is grown first, and then a layer of HfO 2 is grown, and the cycle is repeated, and the last layer of ZrO 2 is capped.
  • the composition ratio of Hf and Zr is 0.6:0.4, and the dielectric thickness is 15nm.
  • an Al 2 O 3 intercalation layer is prepared by an ALD process, and trimethyl aluminum is selected as the precursor of Al, and deionized water is used as the oxygen source.
  • the deposition temperature is 290°C
  • the Al precursor and deionized water are kept at a room temperature of 20°C
  • the carrier gas is N 2
  • the gas flow rate is 70 sccm
  • the thickness of the Al 2 O 3 intercalation layer can be 2 nm.
  • a Pd metal protective layer a Pd target, a beam current voltage of 900V, a beam current of 60mA, an acceleration voltage of 170V, an Ar gas, a flow rate of 9 sccm, and a metal protective layer thickness of 30nm.
  • the above operation will be obtained by having a substrate layer, an electrode, a dielectric layer, Al 2 O 3 layer is interposed, the upper electrode, HfO 2 electrical component iron metal protective layer to the photoresist and excess metal immersed in an acetone solution Fall off; then soak in absolute ethanol to remove acetone; then rinse with deionized water and blow dry.
  • HfO 2 -based ferroelectric devices were annealed under N 2 atmosphere at 450° C. for 20 s to obtain HfO 2 -based ferroelectric capacitors.

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Abstract

一种HfO2基铁电电容器及其制备方法和HfO2基铁电存储器，属于微电子技术领域，通过在铁电电容的介质层和上电极（TiN）之间插入热膨胀系数小于TiN的Al2O3插层，达到增大铁电存储器存储窗口的目的。HfO2基铁电电容器，从下到上包括衬底层（1）、下电极（2）、介质层（3）、Al2O3插层（4）、上电极（5）和金属保护层（6）。可提高存储窗口大小，有效防止信息误读，从而提高存储器的可靠性。

Description

一种HfO 2基铁电电容器及其制备方法和HfO 2基铁电存储器 技术领域
本申请属于微电子技术领域，特别涉及一种HfO 2基铁电电容器及其制备方法和HfO 2基铁电存储器。
背景技术
随着集成电路产业的发展，代表当今半导体非易失性存储器先进水平的闪存器件，尽管有新型结构和设计方案不断涌现，依然面临着诸如读写速度慢、操作电压高、循环次数有限以及尺寸缩放极限等问题。相比于对传统闪存器件的改进和发展，多种新型非易失性存储器也在广泛研究中。铁电随机存取存储器(FeRAM)是这其中具有代表性的新型器件。铁电存储器单元结构和动态随机存取存储器(DRAM)相似，由一个场效应晶体管(MOSFET)和一个铁电电容器组成。铁电电容器是其中存储信息的部分，由上下电极和介质层组成三明治结构，其介质层具有铁电性，存在极化回滞曲线，利用铁电畴的极化方向代表二进制“0”和“1”存储信息，其剩余极化强度值代表了存储器的存储窗口大小。铁电畴的极化翻转时间在纳秒量级，因此铁电存储器的写入速度较快，且能耗较低。
传统钙钛矿结构的铁电材料存在诸多缺陷。首先其化学成分复杂，制备难度较大，且不能和现有的CMOS工艺兼容；其次钙钛矿结构的铁电材料禁带宽度相对较小，为了保证漏电流水平，薄膜的厚度难以微缩到现有工艺节点水平；部分钙钛矿铁电材料，如钛酸锆铅(PZT)，其成分中含有有毒物质铅，因此被部分国家禁用。传统铁电材料由于这些缺陷的限制，始终难以正式走向市场应用。近期提出的基于掺杂HfO 2的新 型铁电材料，因为其成熟的原子层淀积(ALD)制备工艺，能与现有标准CMOS工艺兼容，并且其禁带宽度比钙钛矿铁电材料大，目前已经证实在5nm左右厚度时仍存在铁电性，从而能应用于3D结构，极大程度提高集成度。因此，HfO2基铁电存储器是极具发展潜力的新一代非易失性半导体存储器。
目前已证实，由于非中心对称的正交相(o相，空间集群Pca2 1)的存在导致了铁电性的出现。常温常压下，HfO 2的本体相为中心对称的单斜相(m相，空间集群P2 1/c)，不具有铁电性。在材料退火结晶的过程中，由于受到非对称的应力作用(主要为竖直方向的拉伸应力和水平方向的压缩应力)，产生了从m相到o相的相变，薄膜出现铁电性。o相的组分比例决定了材料铁电性的强弱，可通过剩余极化强度(P r)直观体现。剩余极化强度是铁电存储器的关键参数之一，通常将2P r视为存储器的存储窗口大小，提高存储窗口大小可以有效防止信息误读，从而提高存储器的可靠性。
发明内容
鉴于以上分析，本申请旨在提供一种HfO 2基铁电电容器及其制备方法和HfO 2基铁电存储器，达到增大铁电存储器存储窗口的目的。本申请对于其他元素(如Si、Y、Gd等)掺杂的HfO 2基铁电存储器同样适用。
本申请的目的主要是通过以下技术方案实现的：
本申请提供了一种HfO 2基铁电电容器，从下到上包括衬底层、下电极、介质层、Al 2O 3插层、上电极和金属保护层。
进一步的，衬底层材料为SiO 2/Si或SiO 2。
进一步的，下电极材料为TiN，厚度为10～60nm。
进一步的，介质层为HZO，Hf和Zr的摩尔组分比例为(0.4～0.6)：(0.4～0.6)，厚度为8～15nm。
进一步的，Al 2O 3插层厚度为2nm～3nm。
进一步的，上电极材料为TiN，厚度为10～60nm。
本申请还提供了一种HfO 2基铁电电容器的制备方法，包括以下步骤：
提供衬底，并清洗衬底；
在清洗完成的衬底上溅射制备下电极；
在下电极上沉积介质层；
在介质层上沉积Al 2O 3插层；
在Al 2O 3插层上涂光刻胶、曝光显影；
在上述处理后的Al 2O 3插层上溅射制备上电极；
在形成的上电极上溅射制备金属保护层；
去除光刻胶和多余金属后退火处理。
进一步的，在Al 2O 3插层上涂光刻胶、曝光显影为：在Al 2O 3插层上涂覆负胶，150℃前烘1min，曝光后120℃后烘1min，在显影液中浸泡30s显影，用去离子水冲洗吹干。
进一步的，去除光刻胶和多余金属包括以下步骤：在丙酮溶液中浸泡至光刻胶和多余金属脱落；在无水乙醇中浸泡去除丙酮；用去离子水冲洗吹干。
本申请还提供了一种HfO 2基铁电存储器，包括HfO 2基铁电电容器或由上述制备方法制备得到的HfO 2基铁电电容器。
与现有技术相比，本申请至少能实现以下技术效果之一：
1)本申请通过在铁电电容器的介质层和上电极(TiN)之间插入热膨胀系数小于TiN的Al 2O 3插层，以此在退火过程中提供更强的拉伸应力作用，从而提高介质中o相的组分比例，最终达到提高剩余极化强度，增大铁电存储器存储窗口的目的，提高存储窗口大小可以有效防止信息误读，从而提高存储器的可靠性。
2)介质层为HZO(铪-锆氧化物)时，Hf和Zr的摩尔组分比例为(0.4～0.6)：(0.4～0.6)，厚度为8～15nm，此时，具有最强的铁电性。
本申请的其他特征和优点将在随后的说明书中阐述，并且，部分可从说明书中变得显而易见，或者通过实施本申请而了解。本申请的目的和其他优点可通过在所写的说明书以及附图中所特别指出的结构来实现和获得。
附图说明
附图仅用于示出具体实施例的目的，而并不认为是对本申请的限制，在整个附图中，相同的附图标记表示相同的部件。
图1为实施例1的HZO铁电电容器的结构示意图；
图2为实施例1的PV特性对比图。
附图标记：
1-衬底层；2-下电极；3-介质层；4-Al 2O 3插层；5-上电极；6-金属保护层。
具体实施方式
以下结合具体实施例对一种HfO 2基铁电电容器及其制备方法和 HfO 2基铁电存储器作进一步的详细描述，这些实施例只用于比较和解释的目的，本申请不限定于这些实施例中。
在附图中示出了根据本公开实施例的各种结构示意图。这些图并非是按比例绘制的，其中为了清楚表达的目的，放大了某些细节，并且可能省略了某些细节。图中所示出的各种区域、层的形状以及它们之间的相对大小、位置关系仅是示例性的，实际中可能由于制造公差或技术限制而有所偏差，并且本领域技术人员根据实际所需可以另外设计具有不同形状、大小、相对位置的区域/层。
在本公开的上下文中，当将一层/元件称作位于另一层/元件“上”时，该层/元件可以直接位于该另一层/元件上，或者它们之间可以存在居中层/元件。另外，如果在一种朝向中一层/元件位于另一层/元件“上”，那么当调转朝向时，该层/元件可以位于该另一层/元件“下”。
一方面，本申请提供了一种HfO 2基铁电电容器，从下到上依次包括衬底层1、下电极2、介质层3、Al 2O 3插层4、上电极5和金属保护层6。
衬底层1材料可以是单独的SiO 2，也可以是从上到下设置的SiO 2/Si。当衬底层1材料是SiO 2/Si时，优选的，SiO 2的厚度为100～500nm，Si的厚度为300～600μm。
下电极2、上电极5的材料均为TiN，优选的，TiN厚度为10nm～60nm，若厚度小于10nm，可能会失去铁电性，大于60nm则造成材料浪费。示例性的，厚度为40nm。介质层3为HfO 2基材料，示例性的，介质层3为HZO(铪-锆氧化物)，Hf和Zr的摩尔组分比例为(0.4～0.6)：(0.4～0.6)，厚度为8～15nm，此时，具有最强的铁电性，示例性的，厚度为10nm。优选的，Hf和Zr的摩尔组分比例为1：1，此时介质层3的铁电性最强。介质层3也可以是其他元素(如Si、Y、Gd等)掺杂的HfO 2基材料。
如图2所示，本申请通过在铁电电容器的介质层和上电极(TiN)之间插入热膨胀系数小于TiN的Al 2O 3插层，以此在退火过程中提供更强的拉伸应力作用，从而提高介质中o相的组分比例，最终达到提高剩余极化强度，增大铁电存储器存储窗口的目的，提高存储窗口大小可以有效防止信息误读，从而提高存储器的可靠性。优选的，Al 2O 3插层4厚度为2nm～3nm。太薄则应力作用不明显，太厚则对器件的电学特性影响较大，如介电干扰，电阻分压等。
金属保护层6材料为Pd、Au、Pt等惰性金属，厚度为10-30nm，示例性的，为20nm。
另一方面，本申请提供了一种HfO 2基铁电电容器的制备方法，包括以下步骤：
步骤1，清洗衬底1：将衬底依次用丙酮、无水乙醇浸泡、清洗、吹干；再用去离子水浸泡冲洗、吹干。
步骤2，在衬底1上，利用离子束溅射工艺溅射制备下电极2。
溅射工艺包括但不限于离子束溅射，直流溅射，反应溅射等。示例性的，采用离子束溅射工艺：TiN靶，束流电压700～900V，束流40～60mA，加速电压150～170V，气体为Ar/N 2混合气体，流速分别为(7～9sccm)/(4～6sccm)。在此工艺范围内可获得较好的薄膜衬度，有利于铁电性的产生。
步骤3，在下电极2上沉积介质层3。
示例性的，利用ALD工艺制备HZO介质层。淀积时，先长一层ZrO 2，再长一层HfO 2，依次循环，最后一层ZrO 2封顶。先驱物及氧源均有其他不同选择，淀积温度范围通常在280-300℃。Zr和Hf的先驱物加热至 100～140℃，去离子水保持20℃室温，载气选择N 2，气体流量40～80sccm。示例性的，Hf的先驱物采用四(乙基甲基氨基)铪(IV)(Tetrakis(ethylmethylamido)hafnium(IV)，TEMAH)，化学式Hf(NCH 3C 2H 5) 4；Zr的先驱物采用四(乙基甲基氨基)锆(IV)(Tetrakis(ethylmethylamido)zirconium(IV)，TEMAZ)，化学式Zr(NCH 3CH 5) 4；采用去离子水作为氧源。
步骤4，利用ALD工艺在介质层3上沉积Al 2O 3插层4。
示例性的，选用三甲基铝(Trimethylaluminum，TMA)，化学式Al(CH 3) 3作为Al的先驱物，去离子水作为氧源，淀积温度280-300℃，Al先驱物和去离子水均保持20℃室温，载气选择N 2，气体流量40～80sccm。
步骤5，涂光刻胶、曝光显影。
具体为：在Al 2O 3插层4上涂覆负胶，150℃前烘1min，曝光后120℃后烘1min，在显影液中浸泡30s显影，用去离子水冲洗吹干。
步骤6，利用溅射工艺溅射制备上电极5；
溅射工艺包括但不限于离子束溅射，直流溅射，反应溅射等。示例性的，采用离子束溅射工艺：TiN靶，束流电压700～900V，束流40～60mA，加速电压150～170V，气体为Ar/N 2混合气体，流速分别为(7～9sccm)/(4～6sccm)。在此工艺范围内可获得较好的薄膜衬度，有利于铁电性的产生。
步骤7，利用溅射工艺溅射制备金属保护层6；
示例性的，采用离子束溅射工艺：Pd靶，束流电压700～900V，束流40～60mA，加速电压150～170V，气体为Ar，流速7～9sccm。
步骤8，去除光刻胶和多余金属。
具体包括以下步骤：
步骤801，在丙酮溶液中浸泡至光刻胶和多余金属脱落；
步骤802，在无水乙醇中浸泡去除丙酮；
步骤803，用去离子水冲洗吹干。
步骤9，退火：在N 2气氛、400-500℃条件下快速热退火，快速热退火时间小于1min，优选的，在20-30s。
本申请还提供了一种HfO 2基铁电存储器，包括上述的HfO 2基铁电电容器。
与现有技术相比，本申请的优点在于：
通过增加Al 2O 3插层，在退火过程中提供更多的拉伸应力，相比较于没有Al 2O 3插层的HZO铁电电容器，介质中o相的组分比例更多，介质剩余极化强度更大，从而达到增大存储器存储窗口的目的。本申请的工艺流程简单，效果明显。
实施例1
一种HfO 2基铁电电容器如图1所示，从下到上依次为衬底层SiO 2/Si1、下电极2、介质层3、Al 2O 3插层4、上电极5、金属保护层6。
一种HfO 2基铁电电容器的制备方法，具体工艺步骤如下：
首先，提供SiO 2/Si衬底，上层SiO 2的厚度为300nm，下层Si的厚度为500μm，然后将衬底依次用丙酮、无水乙醇浸泡清洗3min，吹干；再用去离子水浸泡冲洗3min，吹干，完成衬底的清洗。
接着，在清洗好的SiO 2/Si衬底上，利用离子束溅射工艺溅射制备TiN下电极，TiN靶，束流电压800V，束流46mA，加速电压160V，气体为Ar/N 2混合气体，流速分别为8sccm/5sccm，TiN下电极厚度可以为40nm。
然后，在溅射完成的下电极上，利用ALD工艺制备HZO介质层，采用TEMAH和TEMAZ作为Hf和Zr的先驱物，采用去离子水作为氧源。淀积温度280℃，Zr和Hf的先驱物加热至120℃，去离子水保持20℃室温，载气选择N 2，气体流量50sccm。沉积时，先长一层ZrO 2，再长一层HfO 2，依次循环，最后一层ZrO 2封顶。淀积速度分别为
Figure PCTCN2020100984-appb-000001
(即
Figure PCTCN2020100984-appb-000002
每循环)(ZrO 2)，
Figure PCTCN2020100984-appb-000003
(即
Figure PCTCN2020100984-appb-000004
每循环)(HfO 2)，从而保证Hf和Zr的化学计量比近似等于1:1，也就是说，Hf和Zr的组分比例为1:1。沉积至介质层的厚度为10nm完成介质层的制备。
接着，在HZO介质层上，利用ALD工艺制备Al 2O 3插层，选用三甲基铝作为Al的先驱物，去离子水作为氧源。淀积温度300℃，Al先驱物和去离子水均保持20℃室温，载气选择N 2，气体流量50sccm，淀积速度
Figure PCTCN2020100984-appb-000005
Al 2O 3插层厚度可以为2nm。
形成Al 2O 3插层后，在Al 2O 3层上涂覆负胶，150℃前烘1min，曝光后120℃后烘1min，在显影液中浸泡30s显影，用去离子水冲洗吹干。
然后，在Al 2O 3插层上利用离子束溅射工艺溅射制备TiN上电极，TiN靶，束流电压800V，束流46mA，加速电压160V，气体为Ar/N 2混合气体，流速分别为8sccm/5sccm，上电极厚度为40nm。
接着，在形成的上电极上利用离子束溅射工艺溅射制备Pd金属保护层，Pd靶，束流电压800V，束流46mA，加速电压160V，气体为Ar，流速8sccm，金属保护层厚度为20nm。
随后，将通过上述操作得到的具有衬底层、下电极、介质层、Al 2O 3 插层、上电极、金属保护层的HfO 2基铁电器件在丙酮溶液中浸泡至光刻胶和多余金属脱落；然后在无水乙醇中浸泡去除丙酮；之后用去离子水冲洗吹干。
最后，将冲洗吹干的HfO 2基铁电器件在N 2气氛、500℃条件下退火30s，得到HfO 2基铁电容器。
实施例2
一种HfO 2基铁电电容器的制备方法，具体工艺步骤如下：
首先，提供SiO 2/Si衬底，上层SiO 2的厚度为200nm，下层Si的厚度为400μm，然后清洗衬底：将衬底依次用丙酮、无水乙醇浸泡清洗5min，吹干；再用去离子水浸泡冲洗5min，吹干，完成衬底的清洗。
接着，在清洗好的SiO 2/Si衬底上，利用离子束溅射工艺溅射制备TiN下电极，TiN靶，束流电压700V，束流40mA，加速电压150V，气体为Ar/N 2混合气体，流速分别为7sccm/4sccm，TiN下电极厚度可以为60nm。
然后，在溅射完成的下电极上，利用ALD工艺制备HZO介质层，采用TEMAH和TEMAZ作为Hf和Zr的先驱物，采用去离子水作为氧源。淀积温度290℃，Zr和Hf的先驱物加热至100℃，去离子水保持20℃室温，载气选择N 2，气体流量60sccm。沉积时，先长一层ZrO 2，再长一层HfO 2，依次循环，最后一层ZrO 2封顶。Hf和Zr的组分比例为0.4:0.6，沉积至介质层的厚度为10nm完成介质层的制备。
接着在HZO介质层上，利用ALD工艺制备Al 2O 3插层，选用三甲基铝作为Al的先驱物，去离子水作为氧源。淀积温度280℃，Al先驱物和去离子水均保持20℃室温，载气选择N 2，气体流量60sccm，Al 2O 3插层厚度可以为3nm。
形成Al 2O 3插层后，在Al 2O 3层上涂覆负胶，150℃前烘1min，曝光 后120℃后烘1min，在显影液中浸泡30s显影，用去离子水冲洗吹干。
然后，在Al 2O 3插层上利用离子束溅射工艺溅射制备TiN上电极，TiN靶，束流电压700V，束流40mA，加速电压150V，气体为Ar/N 2混合气体，流速分别为7sccm/4sccm，上电极厚度为60nm。
接着，在形成的上电极上利用离子束溅射工艺溅射制备Pd金属保护层，Pd靶，束流电压700V，束流40mA，加速电压150V，气体为Ar，流速7sccm，金属保护层厚度为10nm。
随后，将通过上述操作得到的具有衬底层、下电极、介质层、Al 2O 3插层、上电极、金属保护层的HfO 2基铁电器件在丙酮溶液中浸泡至光刻胶和多余金属脱落；然后在无水乙醇中浸泡去除丙酮；之后用去离子水冲洗吹干。
最后，将冲洗吹干的HfO 2基铁电器件在N 2气氛、400℃条件下退火25s，得到HfO 2基铁电容器。
实施例3
一种HfO 2基铁电电容器的制备方法，具体工艺步骤如下：
首先，提供SiO 2/Si衬底，上层SiO 2的厚度为400nm，下层Si的厚度为600μm，然后清洗衬底：将衬底依次用丙酮、无水乙醇浸泡清洗3min，吹干；再用去离子水浸泡冲洗3min，吹干，完成衬底的清洗。
接着，在清洗好的SiO 2/Si衬底上，利用离子束溅射工艺溅射制备TiN下电极，TiN靶，束流电压900V，束流60mA，加速电压170V，气体为Ar/N 2混合气体，流速分别为9sccm/6sccm，TiN下电极厚度可以为20nm。
然后，在溅射完成的下电极上，利用ALD工艺制备HZO介质层，采用TEMAH和TEMAZ作为Hf和Zr的先驱物，采用去离子水作为氧源。淀积温度300℃，Zr和Hf的先驱物加热至140℃，去离子水保持20℃ 室温，载气选择N 2，气体流量70sccm。沉积时先长一层ZrO 2，再长一层HfO 2，依次循环，最后一层ZrO 2封顶。Hf和Zr的组分比例为0.6:0.4，介质厚度为15nm。
接着在HZO介质层上，利用ALD工艺制备Al 2O 3插层，选用三甲基铝作为Al的先驱物，去离子水作为氧源。淀积温度290℃，Al先驱物和去离子水均保持20℃室温，载气选择N 2，气体流量70sccm，Al 2O 3插层厚度可以为2nm。
形成Al 2O 3插层后，在Al 2O 3层上涂覆负胶，150℃前烘1min，曝光后120℃后烘1min，在显影液中浸泡30s显影，用去离子水冲洗吹干。
然后，在Al 2O 3插层上利用离子束溅射工艺溅射制备TiN上电极，TiN靶，束流电压900V，束流60mA，加速电压170V，气体为Ar/N 2混合气体，流速分别为9sccm/6sccm，上电极厚度为20nm。
接着，在形成的上电极上利用离子束溅射工艺溅射制备Pd金属保护层，Pd靶，束流电压900V，束流60mA，加速电压170V，气体为Ar，流速9sccm，金属保护层厚度为30nm。
随后，将通过上述操作得到的具有衬底层、下电极、介质层、Al 2O 3插层、上电极、金属保护层的HfO 2基铁电器件在丙酮溶液中浸泡至光刻胶和多余金属脱落；然后在无水乙醇中浸泡去除丙酮；之后用去离子水冲洗吹干。
最后，将冲洗吹干的HfO 2基铁电器件在N 2气氛、450℃条件下退火20s，得到HfO 2基铁电容器。
在以上的描述中，对于各层的构图、刻蚀等技术细节并没有做出详细的说明。但是本领域技术人员应当理解，可以通过各种技术手段，来 形成所需形状的层、区域等。另外，为了形成同一结构，本领域技术人员还可以设计出与以上描述的方法并不完全相同的方法。另外，尽管在以上分别描述了各实施例，但是这并不意味着各个实施例中的措施不能有利地结合使用。
以上所述，仅为本申请较佳的具体实施方式，但本申请的保护范围并不局限于此，任何熟悉本技术领域的技术人员在本申请揭露的技术范围内，可轻易想到的变化或替换，都应涵盖在本申请的保护范围之内。

Claims (10)

  1. 一种HfO 2基铁电电容器，其特征在于，从下到上依次包括衬底层(1)、下电极(2)、介质层(3)、Al 2O 3插层(4)、上电极(5)和金属保护层(6)。
  2. 根据权利要求1所述的HfO 2基铁电电容器，其特征在于，所述衬底层(1)材料为SiO 2/Si或SiO 2。
  3. 根据权利要求1所述的HfO 2基铁电电容器，其特征在于，所述下电极(2)材料为TiN，厚度为10～60nm。
  4. 根据权利要求1所述的HfO 2基铁电电容器，其特征在于，所述介质层(3)为HZO，Hf和Zr的摩尔组分比例为(0.4～0.6)：(0.4～0.6)，厚度为8～15nm。
  5. 根据权利要求1所述的HfO 2基铁电电容器，其特征在于，所述Al 2O 3插层(4)厚度为2nm～3nm。
  6. 根据权利要求1-5所述的HfO 2基铁电电容器，其特征在于，所述上电极(5)材料为TiN，厚度为10～60nm。
  7. 一种HfO 2基铁电电容器的制备方法，其特征在于，包括以下步骤：
    提供衬底，并清洗衬底(1)；
    在清洗完成的衬底(1)上溅射制备下电极(2)；
    在下电极(2)上沉积介质层(3)；
    在介质层(3)上沉积Al 2O 3插层(4)；
    在Al 2O 3插层(4)上涂光刻胶、曝光显影；
    在上述处理后的Al 2O 3插层(4)上溅射制备上电极(5)；
    在形成的上电极(5)上溅射制备金属保护层(6)；
    去除光刻胶和多余金属后退火处理。
  8. 根据权利要求7所述的HfO 2基铁电电容器的制备方法，其特征在于，所述在Al 2O 3插层(4)上涂光刻胶、曝光显影为：在Al 2O 3插层(4)上涂覆负胶，150℃前烘1min，曝光后120℃后烘1min，在显影液中浸泡30s显影，用去离子水冲洗吹干。
  9. 根据权利要求7所述的HfO 2基铁电电容器的制备方法，其特征在于，去除光刻胶和多余金属包括以下步骤：在丙酮溶液中浸泡至光刻胶和多余金属脱落；在无水乙醇中浸泡去除丙酮；用去离子水冲洗吹干。
  10. 一种HfO 2基铁电存储器，其特征在于，包括权利要求1-6任一项所述的HfO 2基铁电电容器或权利要求7-9任一项所述的制备方法制备得到的HfO 2基铁电电容器。
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