CN108707879A - A kind of preparation method and application of hafnium doped ZrO 2 ferroelectric thin film - Google Patents

A kind of preparation method and application of hafnium doped ZrO 2 ferroelectric thin film Download PDF

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CN108707879A
CN108707879A CN201810342651.7A CN201810342651A CN108707879A CN 108707879 A CN108707879 A CN 108707879A CN 201810342651 A CN201810342651 A CN 201810342651A CN 108707879 A CN108707879 A CN 108707879A
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thin film
ferroelectric thin
hafnium
substrate
preparation
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周大雨
王静静
董伟
王雪霞
马晓倩
姚凡
姚一凡
李帅东
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Dalian University of Technology
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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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    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
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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
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/125—Process of deposition of the inorganic material
    • C23C18/1254—Sol or sol-gel processing
    • 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
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/125—Process of deposition of the inorganic material
    • C23C18/1295—Process of deposition of the inorganic material with after-treatment of the deposited inorganic material

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Abstract

The present invention provides a kind of preparation method and applications of hafnium doped ZrO 2 ferroelectric thin film.The full-inorganic hafnium doped ZrO 2 (ZrHfO of clear is prepared using inorganic zirconium salts, inorganic hafnium salt as presoma first2) precursor solution；Then according to ZrHfO2Precursor solution repeatedly can be coated in the substrate surface after the cleaning of standard RCA clean technique and obtain orthorhombic phase Pca2 through drying, the pre-heat treatment, short annealing crystallization by the thickness requirement of film1The ZrHfO of space group crystal structure2Ferroelectric thin film.The method have the characteristics that：Film thickness controllable precise, compactness is good, at film uniformity is good, surface roughness is small, crystallite dimension is small；Of low cost, equipment and operating environment require simply, and doped chemical content is flexibly controllable, simple production process, and good process repeatability is easily industrialized production.

Description

A kind of preparation method and application of hafnium doped ZrO 2 ferroelectric thin film
Technical field
The invention belongs to field of microelectronic devices, and in particular to a kind of to prepare hafnium doping two using full-inorganic precursor solution The method of zirconium oxide ferroelectric thin film and application.
Background technology
Ferroelectric memory has many advantages, such as non-volatile, low-power consumption, high storage density, high read or write speed, strong radioresistance, There is boundless application prospect, the most research of forefathers to concentrate on perovskite structure base for electronic information and national defence Material system.Traditional perovskite structure ferroelectric material because with metal-oxide semiconductor (MOS) (CMOS) integrated technique technical compatibility Difference seriously constrains the development of the Research of Integrated Ferroelectric Devices such as ferroelectric memory with the shortcomings of prepared by 3-D nano, structure is difficult to realize, anxious New alternative materials need to be developed.With ZrO2For representative binary oxide high-k (height-k) thin-film material from last century 90 As research hotspot from age, and in replacing SiO extensively in microelectronics industry in recent years2As transistor gate medium and dynamic Random access memory (DRAM) condenser dielectric.In recent years, ZrO2The super large that is found to be of base film ferroelectric property integrates density ferroelectric The research and application of device bring new development opportunity, it is contemplated that the new breakthrough that ferroelectric memory will be brought to study.
ZrO is prepared at present2The method of base film is varied, includes mainly magnetron sputtering method, chemical vapour deposition technique, original Sublayer sedimentation and sol-gel method etc..Have that equipment is simple, experimental cost is cheap due to Preparation of Thin Films by Sol-Gel Method and Chemical constituent controls the advantages that being easy and receives people's favor.However conventional sol-gel processes prepare ZrO2Film is dependent on shape At big sol particles, the deposition rate of film is all larger, and film thickness requires to be restricted；And with organic using metal during glue Reagent, cause to be densified between particle needed for activation energy height and organic residue cannot drive away completely, be easy to generate highly porous film, The defects of film leakage current density is larger does not meet the requirement of thin-film electro aspect of performance.S.Starchich et al. is in article “Ferroelectric and piezoelectric properties of H1-xZrxO2and pure ZrO2films, Hafnium doped ZrO 2 base iron is prepared using CSD methods in Applied Physics Letters, 110,182905 (2017) " Conductive film, the wherein preparation of precursor solution with 2,4- pentadienes zirconium, 2,4- acetylacetone,2,4-pentanediones hafnium and anhydrous organic solvent be raw material, It is expensive, and all operations must carry out in the glove box for having inert gas shielding, environmental condition requires harsh.Jiang Kai et al. is in article " Low-Energy Path to Dense HfO2Thin Films with Aqueous Precursor, With inorganic salts HfOCl in Chemistry of Materials, 23 (4), 945-952 (2011) "2·8H2O is raw material, and use is molten Glue-gel method prepares the sol particles of nanoscale, and prepares non-impurity-doped HfO using spin coating coating process2Film moves back Single low symmetrical monocline (m) phase structure is all presented in film after fiery crystallization, and film does not have ferroelectric property.And Jiang Only to HfO in article2Preparation, since Zr with Hf physicochemical properties are similar, by improving preparation process, the present invention is by nothing Chemical machine solution-deposition method, which is expanded, to be applied to prepare ZrO2On based ferroelectric film, pass through introducing (addition) doped chemical hafnium, control The methods of film thickness and subsequent annealing technological parameter realize orthorhombic phase (o, the Pca2 of high symmetry1), tetragonal phase (t, P42/ Nmc), the stabilization of cubic phase (c, Fm3m) or its mixed phase at room temperature, it is initial intrinsic or can be outside to make film have The lower ferroelectric property generated of field induction.
The present invention overcomes above-mentioned traditional shortcoming, and the preparation of precursor solution is all using water-soluble inorganic reagent, without organic Object participates in, and entire experimental implementation completes under atmosphere at room temperature environment, have cost of material is low, equipment and environmental requirement are simple, The advantages that doped chemical content is flexibly controllable, ferroelectric property is easy to regulation and control, good process repeatability, to carry out ZrHfO2Ferroelectric thin film Magnanimity prepare and performance study open completely new approach.
Invention content
It is an object of the invention to overcome above-mentioned the deficiencies in the prior art, a kind of hafnium doped ZrO 2 ferroelectric thin is provided The preparation method and application of film.
The present invention is achieved by the following technical solutions：Hafnium is prepared as presoma using inorganic zirconium salts, inorganic hafnium salt first Then doped ZrO 2 precursor solution is surface-treated the substrate after the cleaning of standard RCA clean technique, then will Precursor solution is coated on substrate, and the hafnium doped ZrO 2 ferroelectricity of crystallization is obtained after drying, the pre-heat treatment, short annealing Film finally prepares top electrode in film surface, obtains metal-ZrHfO2Ferroelectric thin film-substrate (MIS) structure capacitance.
The present invention includes the following steps：
1) precursor solution is prepared：Using inorganic zirconium salts and inorganic hafnium salt as raw material, the wherein doping concentration of hafnium is 1- The mixed solution A of raw material and deionized water is stirred at room temperature 2-3 hours 50mol%, states alkalinity is added in solution A then up Precipitating reagent generates white precipitate, and the range of control ph then precipitates 5-6 within 7.0-9.0 with deionized water eccentric cleaning It is secondary, obtain precipitate B, into above-mentioned precipitate B be added acid, obtain mixed liquor C, by mixed liquor C persistently stir 10-12 hours to get To the hafnium doped ZrO 2 precursor solution of clear, the pH value for controlling clear sol is less than 1.0；
2) substrate cleaning and surface treatment：Using standard RCA cleanings clean substrate, then by dry substrate into Row surface preparation, to increase the wetability of substrate surface and precursor solution；
3) it coats and is dried：By above-mentioned steps 1) in obtained precursor solution be coated in the substrate after step 2) On, after substrate surface deposits thin film, places the substrate on 120-170 DEG C of hot plate and heats 1-3min, repeat the above steps, Until film thickness needed for obtaining；
4) film is heat-treated：The above-mentioned film 3) obtained is placed in roasting glue machine and carries out the pre-heat treatment, with 0.5-3 DEG C/min Heating rate be heated to 380-420 DEG C, then, the film that the pre-heat treatment is crossed quickly is moved back under the protection of purification gas Fire processing obtains the hafnium doped ZrO 2 ferroelectric thin film of crystalline state.
Further, above-mentioned steps 1) described in inorganic zirconium salts be ZrOCl2·8H2O、Zr(NO3)4·xH2O、ZrO (NO3)2·xH2O、ZrCl4、Zr(SO4)2In one kind；Inorganic hafnium salt is HfOCl2·8H2O、Hf(NO3)4·xH2O、HfO (NO3)2·xH2O、HfCl4、Hf(SO4)2One kind in aqueous inorganic salt；Alkaline precipitating agent is NH3·H2O, NaOH, KOH, urine One kind in element, ammonium hydrogen carbonate；Acid is monoacid HX, HX HNO3, one kind in HCOOH, and the molar ratio of X/Zr is 1.1- 1.5。
Further, above-mentioned steps 1) in acid mixing hydrogen peroxide be added precipitation in, hydrogen peroxide is as cosolvent, favorably It is dissolved in accelerating precipitation.
Further, above-mentioned steps 1) described in alkaline precipitating agent and Zr4+Molar concentration rate be 3.5~2.5:1.
Further, above-mentioned steps 1) described in precursor solution in Zr4+Concentration pass through the deionized water of addition Amount is adjusted between 0.01-0.6mol/L, can be used for controlling the thickness of film.
Further, above-mentioned steps 2) described in substrate using one kind in Si, Ge or GaAs semi-conducting material；It is described Substrate pretreatment mode is ultraviolet irradiation or plasma bombardment.
Further, above-mentioned steps 3) described in painting method be spin coating, dip-coating, one kind in spraying.
Further, above-mentioned steps 3) described in coating and be dried step can be repeatedly more according to film thickness demand Secondary progress, then carries out subsequent thin film heat treatment again, can control the thickness of film；The hafnium doped ZrO 2 ferroelectric thin The thickness of film is within 10-400nm.
Further, above-mentioned steps 4) described in short annealing treatment process parameter be：With the heating speed of 5-10 DEG C/s Degree is heated to 400-500 DEG C, keeps the temperature 5-10min, then be heated to 500-900 DEG C with the heating rate of 10-50 DEG C/s, keeps the temperature 10- Cool to room temperature after 90s with the furnace；The purification gas is one kind in nitrogen, oxygen, argon gas.
The application of hafnium doped ZrO 2 ferroelectric thin film prepared by the above method, by the hafnium doped ZrO 2 ferroelectric thin Film is integrated into capacitor arrangement, and electrical performance testing is carried out to it using ferroelectricity tester；Wherein, capacitor arrangement is metal Top electrode-ZrHfO2Ferroelectric thin film-substrate (MIS) structure, electrode of metal-ZrHfO2Ferroelectric thin film-metallic bottom electrode-substrate (MIM) structure, polysilicon-ZrHfO2Ferroelectric thin film-substrate (SIS) structure or polysilicon-ZrHfO2Ferroelectric thin film-metal bottom electricity One kind in pole-substrate (SIM) structure capacitance.
Further, the capacitor arrangement in above application is electrode of metal-ZrHfO2Ferroelectric thin film-substrate (MIS) Structure capacitance, the electrode of metal are titanium nitride (TiN), tantalum nitride (TaN), platinum (Pt), golden (Au), iridium (Ir), aluminium (Al), one kind in copper (Cu)；The top electrode thickness is 50-150nm, and the substrate is the semiconductors such as Si, Ge or GaAs One kind in material.
Further, the capacitor arrangement in above application is electrode of metal-ZrHfO2Ferroelectric thin film-metal bottom electricity Pole-substrate (MIM) structure capacitance, the electrode of metal and hearth electrode are titanium nitride (TiN), tantalum nitride (TaN), platinum (Pt), one kind in golden (Au), iridium (Ir), aluminium (Al), copper (Cu)；The top electrode thickness is 50-150nm, the substrate For one kind in the materials such as the semiconductor chips such as Si, Ge or GaAs or glass, ceramics.
Further, the capacitor arrangement in above application is polysilicon-ZrHfO2Ferroelectric thin film-substrate (SIS) structure Capacitor, the substrate are one kind in the semi-conducting materials such as Si, Ge or GaAs.
Further, the capacitor arrangement in above application can be polysilicon-ZrHfO2Ferroelectric thin film-metal bottom electricity Pole-substrate (SIM) structure capacitance, the metallic bottom electrode be titanium nitride (TiN), tantalum nitride (TaN), platinum (Pt), golden (Au), One kind in iridium (Ir), aluminium (Al), copper (Cu)；The substrate is the semiconductor chips or glass, ceramics etc. such as Si, Ge or GaAs One kind in material.
Further, the method that top electrode clamping may be used in the annealing process in above-mentioned steps four is preparing hafnium doping After zirconium dioxide membrane, top electrode is deposited first, then carries out short annealing processing.
The present invention prepares hafnium doped ZrO 2 precursor solution using full-inorganic chemical solution method, by controlling film The technological parameters such as thickness, doped chemical content, annealing process, obtain containing be stabilized at room temperature orthorhombic phase (o, Pca21), tetragonal phase (t, P42/ nmc), the hafnium doped ZrO 2 ferroelectric thin film of cubic phase (c, Fm3m) or its mixed phase, and this The film thickness controllable precise of method preparation, compactness is good, good at film uniformity, surface roughness is low.
Compared with prior art, the present invention has the following advantages：
(1) present invention uses full-inorganic precursor solution preparation method, using inorganic salts presoma as raw material, in entire colloidal sol It is participated in without organic matter in preparation process, environmental pollution is low, and human body damage is small, and cost of material is low.
(2) in the present invention, equipment and environmental requirement are simple, are not required to the filming equipment of complex and expensive, experimental implementation is in room It is completed under warm atmospheric environment, reduces the rigors to operating environment, it is energy saving, it is easy to operate, it is suitble to mass production.
(3) film thickness is controlled by changing the concentration, film deposition cycle, spin coating proceeding parameter of thin precursor solution, Simple for process, process control can meet different demands.
(4) doping content of high symmetrical phase hafnium salt stabilizing agent is easy to operate, flexibly controllable.
(5) in rta technique, the ferroelectricity orthorhombic phase that the clamping action that does not need top electrode can be in stabilizing films, Greatly simplify the preparation process of ferroelectric thin film.
Description of the drawings
Fig. 1 is hafnium doped ZrO 2 ferroelectric thin film preparation technology flow chart in the method for the present invention.
Fig. 2 is that Hf adulterates ZrO in embodiment 12It is 40mol%, film thickness 15nm, the XRD diagram of sample in doping Spectrum, wherein o represent orthorhombic phase, and m represents monoclinic phase.
Fig. 3 is that Hf adulterates ZrO in embodiment 12It is 40mol%, film thickness 15nm, the AFM shapes of sample in doping Looks figure.
Fig. 4 is that Hf adulterates ZrO in embodiment 22It is 40mol% in doping, the electric hysteresis of film thickness 10nm, sample return Line chart.
Specific implementation mode
The various illustrative case study on implementation of the present invention are described below.To make the objectives, technical solutions, and advantages of the present invention It is more clear, the operating process of the present invention is described in further detail below in conjunction with attached drawing and specific example.
Embodiment 1
A method of hafnium doped ZrO 2 ferroelectric thin film being prepared using full-inorganic precursor solution, it includes following step Suddenly：
(1) ZrO that Hf doping concentrations are 40mol% is prepared2Base precursor solution：By ZrOCl2·8H2O、HfOCl2· 8H2O precursor materials are completely dissolved in deionized water, while stirring the suitable 1mol/L of fast drop into above-mentioned solution Ammonium hydroxide generates white precipitate (pH=8.5), is then precipitated 5 times with deionized water centrifuge washing, remaining chlorine in being precipitated with removal Ion (Cl-), finally by appropriate 2mol/L nitric acid (HNO3) and 10mol/L hydrogen peroxide (H2O2) be mixed to form degumming agent, be added from In precipitation after the heart, continuing magnetic force stir about 12h obtains the colloidal sol of clear, a concentration of 0.1mol/ after standing a period of time L (pH=0.7)；
(2) it selects p-Si substrates as substrate, is cleaned using standard RCA clean technique, then will be after clean dried Substrate carries out plasma bombardment, to increase its wetability with colloidal sol；
(3) it uses spin coating proceeding that above-mentioned colloidal sol is coated in silicon substrate surface, is subsequently placed on 150 DEG C of hot plates and heats 1min repeats the above steps, until obtaining the film that film thickness is 15nm；
(4) substrate after above-mentioned plated film is placed in roasting glue machine and carries out the amorphous film of the pre-heat treatment acquisition, technique ginseng Number is：380 DEG C are heated to the heating rate of 2 DEG C/min, keeps the temperature 5min；Then the film after the pre-heat treatment is placed in and is quickly moved back In stove, in N2Protection is lower to carry out short annealing crystallization：It is heated to 450 DEG C with the heating rate of 10 DEG C/s, keeps the temperature 5min, then with The heating rate of 30 DEG C/s is heated to 650 DEG C, and room temperature is cooled to the furnace after keeping the temperature 30s, obtains the Hf doping ZrO of crystalline state2Base iron Conductive film, and film surface is smooth, smooth, and without apparent stomata and crackle, rms surface roughness is only 0.12nm, sample XRD spectrum and AFM the patterns difference of product are as shown in Figures 2 and 3；
(5) the TiN top electrodes for using Radiofrequency muti-hook probe deposition 80nm, obtain MIS structure capacitor.Finally use iron The electric property of electric tester test capacitors.
Embodiment 2
Selection p-Ge substrates are substrate, and the TiN hearth electrodes of 10nm are prepared using Radiofrequency muti-hook probe, and it is thick to prepare 10nm ZrHfO2Ferroelectric thin film, remaining processing step and process conditions are same as Example 1, obtain metal-ZrHfO2Ferroelectric thin film- Metal type capacitor, using the ferroelectric properties of ferroelectricity tester test capacitors, ferroelectric hysteresis loop is as shown in Figure 4.
Embodiment 3
Preparation hafnium doping concentration is 2mol%, and collosol concentration is the hafnium doped ZrO 2 precursor solution of 0.6mol/L, Selection p-Ge substrates are substrate, the TiN hearth electrodes of 10nm are prepared using Radiofrequency muti-hook probe, short annealing crystallization temperature is 900 DEG C, prepare the ZrHfO of 390nm thickness2Ferroelectric thin film, remaining processing step and process conditions are same as Example 1, obtain gold Category-ZrHfO2Ferroelectric thin film-metal type capacitor utilizes the ferroelectric properties of ferroelectricity tester test capacitors.
Embodiment 4
Select ZrCl4、HfCl4For precursor material, preparation Hf doping concentrations are 2mol%, collosol concentration 0.5mol/L ZrO2Base precursor solution selects p-Si substrates as substrate, and short annealing crystallization temperature is 600 DEG C, prepares 380nm thickness ZrHfO2Ferroelectric thin film, remaining processing step and process conditions are same as Example 1, obtain MIS structure capacitor, utilize ferroelectricity The ferroelectric properties of tester test capacitors.
Embodiment 5
Selection p-Ge substrates are substrate, and the TiN hearth electrodes of 10nm are prepared using Radiofrequency muti-hook probe, and short annealing is brilliant It is 900 DEG C to change temperature, and hafnium doping concentration is the ZrHfO that 45mol% prepares 10nm thickness2Ferroelectric thin film, remaining processing step and work Skill condition is same as Example 1, obtains metal-ZrHfO2Ferroelectric thin film-metal type capacitor tests electricity using ferroelectricity tester The ferroelectric properties of container.
Embodiment 6
Select ZrOCl2·8H2O、HfCl4For precursor material, preparation Hf doping concentrations are 40mol%, and collosol concentration is The hafnium doped ZrO 2 precursor solution of 0.2mol/L selects p-Ge substrates as substrate, selects Radiofrequency muti-hook probe The TiN hearth electrodes of 10nm are prepared, the method for selecting top electrode clamping, first on the TiN with Radiofrequency muti-hook probe deposition 80nm Electrode, then 700 DEG C of short annealing crystallization, prepare the ZrHfO of 15nm thickness2Ferroelectric thin film, remaining processing step and process conditions with Embodiment 1 is identical, obtains metal-ZrHfO2Ferroelectric thin film-metal type capacitor utilizes the iron of ferroelectricity tester test capacitors Electrical property.
Above-described embodiment combination attached drawing and embodiment 1 and the combination attached drawing of embodiment 2 are similar, so remaining above each implementation Example is provided with embodiment 1 and embodiment 2 for representative in conjunction with attached drawing.

Claims (10)

1. a kind of preparation method of hafnium doped ZrO 2 ferroelectric thin film, which is characterized in that include the following steps：
1) precursor solution is prepared：Using inorganic zirconium salts and inorganic hafnium salt as raw material, wherein the doping concentration of hafnium is 1-50mol%, The mixed solution A of raw material and deionized water is stirred at room temperature, states alkaline precipitating agent is added in solution A then up, generates white Precipitation, control ph are then precipitated with deionized water eccentric cleaning within 7.0-9.0, precipitate B are obtained, into above-mentioned precipitate B Acid is added, obtains mixed liquor C, mixed liquor C is persistently stirred to get to the hafnium doped zirconia (ZrHfO of clear2) forerunner Liquid solution, the pH value for controlling clear sol are less than 1.0；
2) substrate cleaning and surface treatment：Substrate is cleaned using the RCA cleanings of standard, dry substrate is then subjected to table Face pre-processes, to increase the wetability of substrate surface and precursor solution；
3) it coats and is dried：By above-mentioned steps 1) in obtained precursor solution be coated on the substrate after step 2), After substrate surface deposits thin film, places the substrate on 120-170 DEG C of hot plate and heat 1-3min, repeat the above steps, until Film thickness needed for obtaining；
4) film is heat-treated：The above-mentioned film 3) obtained is subjected to the pre-heat treatment, is heated to the heating rate of 0.5-3 DEG C/min 380-420 DEG C, then, the film that the pre-heat treatment is crossed is subjected to short annealing under the protection of purification gas and handles to obtain crystalline state Hafnium doped ZrO 2 ferroelectric thin film.
2. a kind of preparation method of hafnium doped ZrO 2 ferroelectric thin film according to claim 1, which is characterized in that above-mentioned Inorganic zirconium salts described in step 1) are ZrOCl2·8H2O、Zr(NO3)4·xH2O、ZrO(NO3)2·xH2O、ZrCl4、Zr (SO4)2In one kind；Inorganic hafnium salt is HfOCl2·8H2O、Hf(NO3)4·xH2O、HfO(NO3)2·xH2O、HfCl4、Hf (SO4)2One kind in aqueous inorganic salt；Alkaline precipitating agent is NH3·H2O, one kind in NaOH, KOH, urea, ammonium hydrogen carbonate； Acid is monoacid HX, HX HNO3, one kind in HCOOH, and the molar ratio of X/Zr is 1.2-1.5.
3. a kind of preparation method of hafnium doped ZrO 2 ferroelectric thin film according to claim 1 or 2, which is characterized in that Acid mixing hydrogen peroxide is added in precipitation in step 1), and hydrogen peroxide is conducive to accelerate precipitation dissolving as cosolvent.
4. a kind of preparation method of hafnium doped ZrO 2 ferroelectric thin film according to claim 1 or 2, which is characterized in that Above-mentioned steps 1) described in alkaline precipitating agent and Zr4+Molar concentration rate be 3.5~2.5:1.
5. a kind of preparation method of hafnium doped ZrO 2 ferroelectric thin film according to claim 1 or 2, which is characterized in that Above-mentioned steps 1) described in precursor solution in Zr4+Concentration by the amount of the deionized water of addition in 0.01-0.6mol/L Between adjust, can be used for controlling the thickness of film.
6. a kind of preparation method of hafnium doped ZrO 2 ferroelectric thin film according to claim 1 or 2, which is characterized in that Above-mentioned steps 2) described in substrate using one kind in Si, Ge or GaAs semi-conducting material；The substrate pretreatment mode is Ultraviolet irradiation or plasma bombardment.
7. a kind of preparation method of hafnium doped ZrO 2 ferroelectric thin film according to claim 1 or 2, which is characterized in that Above-mentioned steps 3) described in painting method be spin coating, dip-coating, one kind in spraying.
8. a kind of preparation method of hafnium doped ZrO 2 ferroelectric thin film according to claim 1 or 2, which is characterized in that Above-mentioned steps 3) described in coating and be dried step then can again be carried out according to the repeated multiple times progress of film thickness demand Subsequent thin film is heat-treated, and can control the thickness of film；The thickness of the hafnium doped ZrO 2 ferroelectric thin film is in 10- Within 400nm.
9. a kind of preparation method of hafnium doped ZrO 2 ferroelectric thin film according to claim 1 or 2, which is characterized in that Above-mentioned steps 4) described in short annealing treatment process parameter be：It is heated to 400-500 DEG C with the heating rate of 5-10 DEG C/s, 5-10min is kept the temperature, then 500-900 DEG C is heated to the heating rate of 10-50 DEG C/s, room is cooled to the furnace after keeping the temperature 10-90s Temperature；The purification gas is one kind in nitrogen, oxygen, argon gas.
10. the application of hafnium doped ZrO 2 ferroelectric thin film prepared by any the methods of claim 1-9, which is characterized in that The hafnium doped ZrO 2 ferroelectric thin film is integrated into capacitor arrangement, electric property is carried out to it using ferroelectricity tester Test；Wherein, capacitor arrangement is electrode of metal-ZrHfO2Ferroelectric thin film-substrate (MIS) structure, electrode of metal- ZrHfO2Ferroelectric thin film-metallic bottom electrode-substrate (MIM) structure, polysilicon-ZrHfO2Ferroelectric thin film-substrate (SIS) structure or Polysilicon-ZrHfO2One kind in ferroelectric thin film-metallic bottom electrode-substrate (SIM) structure capacitance.
CN201810342651.7A 2018-04-17 2018-04-17 A kind of preparation method and application of hafnium doped ZrO 2 ferroelectric thin film Pending CN108707879A (en)

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CN109574658A (en) * 2018-12-07 2019-04-05 中北大学 A kind of preparation method and application of ferroelectric thin film
CN110648902A (en) * 2019-10-19 2020-01-03 湘潭大学 Preparation method and application of lanthanum-doped hafnium oxide ferroelectric film
CN116217227A (en) * 2023-01-31 2023-06-06 中国科学院赣江创新研究院 Zirconium hafnium oxide ceramic and preparation method and application thereof

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CN109574658A (en) * 2018-12-07 2019-04-05 中北大学 A kind of preparation method and application of ferroelectric thin film
CN110648902A (en) * 2019-10-19 2020-01-03 湘潭大学 Preparation method and application of lanthanum-doped hafnium oxide ferroelectric film
CN116217227A (en) * 2023-01-31 2023-06-06 中国科学院赣江创新研究院 Zirconium hafnium oxide ceramic and preparation method and application thereof
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