CN105603395A - Method for preparing CaCu3Ti4O12 thin films - Google Patents

Method for preparing CaCu3Ti4O12 thin films Download PDF

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CN105603395A
CN105603395A CN201610031323.6A CN201610031323A CN105603395A CN 105603395 A CN105603395 A CN 105603395A CN 201610031323 A CN201610031323 A CN 201610031323A CN 105603395 A CN105603395 A CN 105603395A
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film
cacu
titanium
copper
preparation
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CN105603395B (en
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林媛
姚光
高敏
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University of Electronic Science and Technology of China
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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
    • 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
    • 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
    • C23C18/1204—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
    • C23C18/1208—Oxides, e.g. ceramics
    • C23C18/1216—Metal oxides
    • 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
    • C23C18/1229—Composition of the substrate
    • C23C18/1245—Inorganic substrates other than metallic

Abstract

The invention discloses a method for preparing CaCu3Ti4O12 thin films, and belongs to the technical field of functional materials. The method includes steps of 1), preparing precursor solution with calcium, copper and titanium by the aid of polymer-assisted deposition processes; 2), carrying out heat treatment on beveled LaAlO3 substrates at the temperatures of 800-1000 DEG C for 1-6 hours to obtain substrates with surfaces which are of step structures; 3), uniformly coating the precursor solution on the surfaces of the substrates by the aid of spin-coating processes after the substrates are treated in the step 2) and drying the substrates to obtain thin film samples with the calcium, the copper and the titanium; 4), carrying out heat treatment on the obtained thin film samples with the calcium, the copper and the titanium and cooling the thin film samples along with furnaces until the temperatures of the thin film samples reach the room temperature so as to obtain the CaCu3Ti4O12 thin films. The method has the advantages that stress of the CCTO thin films is regulated and controlled by the aid of the beveled substrates with different beveling angles, and accordingly dielectric loss of the thin films prepared by the aid of the method can be obviously reduced; the method is simple and is low in cost, excellent in process controllability and repeatability and favorable for mass production on a large scale.

Description

A kind of CaCu3Ti4O12The preparation method of film
Technical field
The invention belongs to technical field of function materials, be specifically related to a kind of by regulation and control LaAlO3The substrate of cutting sth. askew shouldPower is prepared low-dielectric loss CaCu3Ti4O12The method of film.
Background technology
The R and D of high dielectric constant material (ε ﹥ 1000) are to realizing application and the electricity of large value capacitorMiniaturization, the microminiaturization of sub-element have great importance. Up to now, some high dielectric constant materialsIn practical devices, be applied. Within 2000, it is found that CaCu3Ti4O12(CCTO) material is at 1kHzUnder AC field effect, dielectric constant can reach 12000, and at certain temperature (100K～600K) and frequency domainIn (0Hz～1MHz) scope, dielectric constant remains unchanged substantially. The high dielectric property of CCTO is once discovery,Cause immediately people's extensive concern, larger but CCTO also has in having high-kDielectric loss, this has also limited the extensive use of CCTO. The at room temperature loss of CCTO polycrystalline ceramics sampleBe 0.067 (100kHz), 0.1 (1kHz), under CCTO film room temperature, loss is 0.2 (10～100kHz),The loss of single crystal samples is higher. But in actual applications, the loss of dielectric substance generally needs to controlBelow 0.05, therefore, in keeping high-k, how to reduce the dielectric loss of CCTO materialThere is great meaning for practical application.
At present, preparation CaCu3Ti4O12(CCTO) the common method of film has physical vapour deposition (PVD) (as radio frequencyMagnetron sputtering, pulsed laser deposition and molecular beam epitaxy etc.), chemical vapour deposition (CVD), sol-gal process and high scoreSub-assistant depositing method etc. First polymer-assistant depositing method forms metal ion binding with water miscible macromoleculeUniform and stable precursor solution, is then evenly coated to precursor solution on substrate, finally by heat treatmentBonding between macromolecule and metal ion is disconnected, and macromolecule decomposes and formation solid film. Compared to preparationThe physical vapour deposition (PVD) of CCTO film and chemical gaseous phase depositing process, polymer-assistant depositing method is to vacuumSpend less demandingly, and there is the advantages such as easy and simple to handle, equipment is simple, low cost. Compared to sol-gel method,Polymer-assistant depositing method has been avoided hydrolysis and the condensation reaction of predecessor, thereby more easily obtains precise chemical structure meterThe stable precursor liquid of amount ratio.
At present, reduce CaCu3Ti4O12(CCTO) method of dielectric loss is mainly doping vario-property, and doping is main(doping ion replaces Cu to be divided into the doping of A position2+And Ca2+) and B position doping (doping ion replacement Ti4+)。But the effect after doping is unsatisfactory, for example, Kobayashi (KobayashiW, TerasakiI.UnusualimpurityeffectsonthedielectricpropertiesofCaCu3-xMnxTi4O12[J].PhysicaB:CondensedMatter, 2003,329:771-772.) etc. use Mn ion replace Cu ion pair CCTO and carry outA position doping, the dielectric loss of material no change substantially and the dielectric constant of material significantly reduces; Bueno(RibeiroWC,AraujoRGC,BuenoPR.Thedielectricsuppressandthecontrolofsemiconductornon-OhmicfeatureofCaCu3Ti4O12bymeansoftindoping[J].AppliedPhysicsLetters, 2011:3.) etc. carry out the doping of B position with Sn, when dielectric loss reduces,Dielectric constant also obviously declines. In addition, Grubbs (GrubbsRK, VenturiniEL, ClemPG, etal.DielectricandmagneticpropertiesofFe-andNb-dopedCaCu3Ti4O12[J].PhysicalReviewB, 104111.) etc. 2005,72 (10): use Nb and Fe ion replace Ti ion pair CCTO and carry out BPosition doping, test result shows, dielectric constant and loss all decline and are subject to the regulation and control of temperature and frequency. Doping changesProperty is had relatively high expectations to process controllability, and process conditions change the repeatability that may affect experiment a little. Therefore,Be badly in need of finding a kind of simple to operate, preparation method of preparing cheaply low-dielectric loss CCTO film.
Summary of the invention
The invention provides a kind of low-dielectric loss CaCu3Ti4O12(CCTO) preparation method of film, the partyMethod is simple to operate, cost is low, the CaCu preparing3Ti4O12Thin-film dielectric loss has significantly reduction.
Technical scheme of the present invention is as follows:
A kind of CaCu3Ti4O12The preparation method of film, comprises the following steps:
Step 1, by polymer-assistant depositing method preparation CaCu3Ti4O12Precursor liquid;
Step 2, LaAlO3The cut sth. askew heat treatment of substrate: by LaAlO3The substrate of cutting sth. askew is put into tube furnace, risesTemperature to 800～1000 DEG C and keep 1～6 hour, is cooled to room temperature with stove, what to obtain surface be ledge structureSubstrate;
Step 3, the precursor liquid that adopts the method for spin coating that step 1 is prepared are evenly coated on step 2 after processingTo the surface substrate surface that is ledge structure, dry, obtain the film sample of calcic copper titanium;
The film sample of step 4, calcic copper titanium that step 3 is obtained is heat-treated, then naturally cold with stoveBut to room temperature, obtain CaCu of the present invention3Ti4O12Film.
Further, LaAlO described in step 23The mis-cut angle of substrate of cutting sth. askew is 1.0 °, 2.5 °, 5.0 °.
Further, polymer-assistant depositing method preparation CaCu described in step 13Ti4O12Precursor liquid concreteProcess is: by mixing with water soluble polymer containing the mixed liquor of calcium salt, mantoquita, titanium salt, obtain calcic network respectivelyCompound mixed liquor, copper-bearing complex mixed liquor, containing titanium complex mixed liquor, then according to containing calcium complex, containCopper complex, the ratio that is 1:3:4 containing the mol ratio of titanium complex, preparation obtains the mixed liquor of calcic copper titanium,As preparation CaCu3Ti4O12The precursor liquid of film. Described water soluble polymer is with amino or imino groupWater-soluble polymer etc. The described concentration containing calcium complex mixed liquor is 0.0002～0.02mol/L.
Further, heat treated gas atmosphere is oxidizing atmosphere described in step 4, is specially with percent by volumeMeter purity is not less than 99.99% pure oxygen, and heat treatment temperature is 800～1000 DEG C, and heat treatment time is 1～6 littleTime.
Beneficial effect of the present invention is: it is 1:3:4 that the present invention adopts polymer-assistant depositing method preparation mol ratioContaining calcium complex, copper-bearing complex, containing the mixed liquor of titanium complex as precursor liquid, then by LaAlO3Cut sth. askew spin coating on substrate, the final film forming of heat treatment. The present invention is by the substrate regulation and control of cutting sth. askew of different mis-cut anglesCaCu3Ti4O12The stress of film, obviously reduces the dielectric loss of the film making; And method is simple,With low cost, there is good process controllability and repeatability, be conducive to large-scale batch production.
Brief description of the drawings
Fig. 1 is schematic flow sheet of the present invention.
Fig. 2 is Embodiment C aCu3Ti4O12(CCTO) X-ray diffraction spectrum of film; (a) CCTO (004)Diffraction maximum scanning spectra; (b) CCTO (004) diffraction maximum fine scanning collection of illustrative plates among a small circle; (c) CCTO (022)Diffraction maximum scanning spectra; (d) CCTO (202) diffraction maximum scanning spectra.
Fig. 3 is Embodiment C aCu3Ti4O12The result of calculation of the lattice paprmeter of film; (a) along a-axisThe lattice paprmeter of ([100]), b-axis ([010]) and c-axis ([001]) direction; (b) the outer lattice paprmeter of face(c-axis) lattice paprmeter (a × b) and in centre plane1/2。
Fig. 4 is Embodiment C aCu3Ti4O12The X ray φ scanning diffraction spectra of film, FWHM is diffraction maximumAverage halfwidth.
Fig. 5 is CaCu prepared by embodiment3Ti4O12The dielectric constant of film and the relation curve of frequency.
Fig. 6 is CaCu prepared by embodiment3Ti4O12The dielectric loss of film and the relation curve of frequency.
Detailed description of the invention
Below in conjunction with drawings and Examples in detail, technical scheme of the present invention is described in detail.
A kind of CaCu3Ti4O12The preparation method of film, comprises the following steps:
Step 1, by polymer-assistant depositing method preparation CaCu3Ti4O12Precursor liquid: respectively will containing calcium salt,The mixed liquor of mantoquita, titanium salt mixes with water soluble polymer, obtains containing calcium complex mixed liquor, copper-bearing complexMixed liquor, containing titanium complex mixed liquor, then according to containing calcium complex, copper-bearing complex, containing titanium complexMol ratio is that the ratio of 1:3:4 is evenly mixed, and preparation obtains the mixed liquor of calcic copper titanium, as preparation CaCu3Ti4O12The precursor liquid of film;
Step 2, LaAlO3The cut sth. askew heat treatment of substrate: by LaAlO3The substrate of cutting sth. askew is put into tube furnace, risesTemperature to 800～1000 DEG C and keep 1～6 hour, is cooled to room temperature with stove, what to obtain surface be ledge structureSubstrate;
Step 3, the precursor liquid that adopts the method for spin coating that step 1 is prepared are evenly coated on step 2 after processingTo the surface substrate surface that is ledge structure, dry, obtain the film sample of calcic copper titanium;
Film sample heat treatment in oxidizing atmosphere of step 4, calcic copper titanium that step 3 is obtained, heat treatmentTemperature is 800～1000 DEG C, and heat treatment time is 1～6 hour, then naturally cools to room temperature with stove, obtainsCaCu of the present invention3Ti4O12Film.
Further, LaAlO described in step 23The mis-cut angle of substrate of cutting sth. askew is 1.0 °, 2.5 °, 5.0 °.
Further, described in step 1, water soluble polymer is the water-soluble polymer with amino or imino groupDeng. The described concentration containing calcium complex mixed liquor is 0.0002～0.02mol/L.
Further, described in step 4 oxidizing atmosphere be in percent by volume purity be not less than 99.99% pureOxygen.
Embodiment 1
A kind of CaCu3Ti4O12The preparation method of film, comprises the following steps:
The precursor solution of step 1, preparation calcic copper titanium, detailed process is:
(1) under normal temperature, in 40mL deionized water, add 1.68g calcium nitrate, be uniformly mixed, soAfter add 3.0g ethylenediamine tetra-acetic acid and 3g water-soluble polymer PEI (polymine), stir, ultrasonicTo solution homogeneous, obtain mixed liquor A; The Amicon8050 type that adopts Millipore company of the U.S. to produce is superFilter device, free ion in elimination mixed liquor A, and evaporation and concentration to obtain concentration be 291.6mmol/L'sCalcic mixed liquor;
(2) under normal temperature, in 40mL deionized water, add 1.93g copper nitrate, be uniformly mixed, soAfter add 3.0g ethylenediamine tetra-acetic acid and 3g water-soluble polymer PEI (polymine), stir, ultrasonicTo solution homogeneous, obtain mixed liquid B; The Amicon8050 type that adopts Millipore company of the U.S. to produce is superFilter device, free ion in elimination mixed liquid B, and evaporation and concentration to obtain concentration be 395.1mmol/L'sCopper-bearing mixture;
(3) under normal temperature, in 40mL deionized water, add 2mL titanium tetrachloride, be uniformly mixed,Then add 2.0g ethylenediamine tetra-acetic acid and 3g water-soluble polymer PEI (polymine), stir, surpassSound, to solution homogeneous, obtains mixed liquor C; The Amicon8050 type that adopts Millipore company of the U.S. to produceUltrafiltration apparatus, free ion in elimination mixed liquor C, and evaporation and concentration to obtain concentration be 311.8mmol/LTitaniferous mixed liquor;
(4) by the calcic mixed liquor of above-mentioned preparation, copper-bearing mixture, titaniferous mixed liquor according to Ca:Cu:Ti=The mixed in molar ratio of 1:3:4 is even, obtains the precursor solution of calcic copper titanium;
Step 2, LaAlO3The cut sth. askew heat treatment of substrate: get mis-cut angle and be the LaAlO of 1.0 °3(001) baseSheet, cleans 15 minutes in acetone, ethanol and deionized water for ultrasonic respectively successively, and nitrogen dries up; To cleanClean substrate, puts into ceramic boat and is pushed to the flat-temperature zone of tube furnace, is warmed up to through 40 minutes by room temperature900 DEG C, be incubated 2 hours, then tube furnace is cooled to room temperature naturally, takes out, and obtains surface for Step-edge JunctionThe substrate of structure;
Step 3, get the precursor solution of the calcic copper titanium that step 1 prepares, process the surface obtaining in step 2Apply the precursor solution of calcic copper titanium for the substrate surface of ledge structure adopts the method for spin coating, evenly dividedThe film sample of the calcic copper titanium precursor thing of cloth, then puts into film sample 30 points of 80 DEG C of insulations of insulating boxClock, takes out stand-by; Wherein, the main process of spin coating is: first pass through low speed rotation, rotating speed is 800r/min,Time is 6s; Then enter High Rotation Speed, rotating speed is 3000r/min, and the time is 30s;
Step 4, film sample after step 3 is dried are put into ceramic boat, and are placed in high temperature process furnances (sectionBrilliant GSL-1200X) flat-temperature zone in, heat-treat, heat treatment temperature is 900 DEG C, the time is 120min,In heat treatment process, gas atmosphere is the pure oxygen taking percent by volume purity as 99.999%; Specifically heat treatedCheng Wei: the heating rate with 1 DEG C/min is warmed up to 510 DEG C by room temperature, at 510 DEG C of insulation 120min; ThenHeating rate with 10 DEG C/min is warming up to 900 DEG C by 510 DEG C, at 900 DEG C of insulation 120min; Finally withThe rate of temperature fall of 10 DEG C/min is down to room temperature by 900 DEG C, takes out sample, obtains of the present inventionCaCu3Ti4O12Film.
Embodiment 2
The difference of the present embodiment and embodiment 1 is: the LaAlO adopting in step 23(001) cutting sth. askew of substrateAngle is 2.5 °, and all the other steps are identical with embodiment 1.
Embodiment 3
The difference of the present embodiment and embodiment 1 is: the LaAlO adopting in step 23(001) cutting sth. askew of substrateAngle is 5 °, and all the other steps are identical with embodiment 1.
Comparative example
A kind of CaCu3Ti4O12The preparation method of film, comprises the following steps:
The precursor solution of step 1, preparation calcic copper titanium, detailed process is:
(1) under normal temperature, in 40mL deionized water, add 1.68g calcium nitrate, be uniformly mixed, soAfter add 3.0g ethylenediamine tetra-acetic acid and 3g water-soluble polymer PEI (polymine), stir, ultrasonicTo solution homogeneous, obtain mixed liquor A; The Amicon8050 type that adopts Millipore company of the U.S. to produce is superFilter device, free ion in elimination mixed liquor A, and evaporation and concentration to obtain concentration be 291.6mmol/L'sCalcic mixed liquor;
(2) under normal temperature, in 40mL deionized water, add 1.93g copper nitrate, be uniformly mixed, soAfter add 3.0g ethylenediamine tetra-acetic acid and 3g water-soluble polymer PEI (polymine), stir, ultrasonicTo solution homogeneous, obtain mixed liquid B; The Amicon8050 type that adopts Millipore company of the U.S. to produce is superFilter device, free ion in elimination mixed liquid B, and evaporation and concentration to obtain concentration be 395.1mmol/L'sCopper-bearing mixture;
(3) under normal temperature, in 40mL deionized water, add 2mL titanium tetrachloride, be uniformly mixed,Then add 2.0g ethylenediamine tetra-acetic acid and 3g water-soluble polymer PEI (polymine), stir, surpassSound, to solution homogeneous, obtains mixed liquor C; The Amicon8050 type that adopts Millipore company of the U.S. to produceUltrafiltration apparatus, free ion in elimination mixed liquor C, and evaporation and concentration to obtain concentration be 311.8mmol/LTitaniferous mixed liquor;
(4) by the calcic mixed liquor of above-mentioned preparation, copper-bearing mixture, titaniferous mixed liquor according to Ca:Cu:Ti=The mixed in molar ratio of 1:3:4 is even, obtains the precursor solution of calcic copper titanium;
Step 2, LaAlO3The heat treatment of substrate: get mis-cut angle and be the LaAlO of 0 °3(001) substrate, complies withInferiorly clean 15 minutes at acetone, ethanol and deionized water for ultrasonic respectively, nitrogen dries up; By clean cleanSubstrate, puts into ceramic boat and is pushed to the flat-temperature zone of tube furnace, is warmed up to 900 DEG C by room temperature through 40 minutes,Be incubated 2 hours, then tube furnace is cooled to room temperature naturally, takes out;
Step 3, get the precursor solution of the calcic copper titanium that step 1 prepares, process the substrate obtaining in step 2Surface adopts the method for spin coating to apply the precursor solution of calcic copper titanium, obtains equally distributed calcic copper titanium precursorThe film sample of thing, then puts into film sample 80 DEG C of insulations of insulating box 30 minutes, takes out stand-by; ItsIn, the main process of spin coating is: first pass through low speed rotation, rotating speed is 800r/min, and the time is 6s; SoAfter enter High Rotation Speed, rotating speed is 3000r/min, the time is 30s;
Step 4, film sample after step 3 is dried are put into ceramic boat, and are placed in high temperature process furnances (sectionBrilliant GSL-1200X) flat-temperature zone in, heat-treat, heat treatment temperature is 900 DEG C, the time is 120min,In heat treatment process, gas atmosphere is the pure oxygen taking percent by volume purity as 99.999%; Specifically heat treatedCheng Wei: the heating rate with 1 DEG C/min is warmed up to 510 DEG C by room temperature, at 510 DEG C of insulation 120min; ThenHeating rate with 10 DEG C/min is warming up to 900 DEG C by 510 DEG C, at 900 DEG C of insulation 120min; Finally withThe rate of temperature fall of 10 DEG C/min is down to room temperature by 900 DEG C, takes out sample, obtains CaCu3Ti4O12Film.
The performance of the CCTO film below embodiment 1,2,3 and comparative example being obtained is analyzed;
Adopt XRD in embodiment 1,2,3 and comparative example at monocrystal chip LaAlO3(001) raw on substrateLong CCTO film carries out θ-2 θ scanning, and result as shown in Figure 2; θ-2 θ scanning by XRD is rightCaCu3Ti4O12/LaAlO3The structure and composition of film is analyzed, and can calculate in face and the outer lattice paprmeter of face,Result as shown in Figure 3; φ by XRD scans CaCu3Ti4O12Film and LaAlO3The extension of substrateRelation characterizes, and result as shown in Figure 4; By Agilent4294A electric impedance analyzer to CaCu3Ti4O12The dielectric properties of film are carried out test analysis, and result as shown in Figure 5 and Figure 6.
As shown in Figure 2, by CaCu3Ti4O12(CCTO) (004) diffraction maximum scanning, CCTO (022) spread outPenetrate peak scanning, the scanning of CCTO (202) diffraction maximum, show at different mis-cut angles (0 °, 1.0 °, 2.5 ° and 5.0 °)The substrate of cutting sth. askew on all prepared CaCu3Ti4O12Film. According to the test result of Fig. 2, can calculateLattice paprmeter (Fig. 3 to film along a-axis ([100]), b-axis ([010]) and c-axis ([001]) direction(a) shown in), and the mean value (shown in Fig. 3 (b)) of the interior lattice paprmeter of face, show that film is along a-axis, b-axisHave different lattice paprmeters with c-axis direction, in the time that mis-cut angle is 2.5 °, the outer lattice of face inner face is normalNumber changes maximum, and in face, the mean value of lattice paprmeter reaches minimum of a value in the time that mis-cut angle is 2.5 °. As figureShown in 4, the halfwidth difference in the φ scanning spectral line of extension CCTO film, the halfwidth of diffraction maximum can showDislocation density in film, halfwidth is less, and dislocation density is less, and then can reduce the loss of dielectric material.As shown in Figure 5, the variation tendency of thin-film dielectric constant is identical with average lattice paprmeter variation tendency in face, and this isBecause the substrate of cutting sth. askew of different angles has different surface step sizes, CCTO film and step dimension suitableJoin and can introduce stretching or compression stress, cause the crystallite dimension of CCTO film increase or reduce. As Fig. 6 instituteShow, the dielectric loss of the film that embodiment 1 obtains in 10KHz～100KHz frequency range isThe dielectric loss of the film that 0.0013～0.005, embodiment 2 obtains in 10KHz～100KHz frequency rangeBe that the dielectric of the film that obtains of 0.0006～0.005, embodiment 3 in 10KHz～100KHz frequency range damagedConsumption is 0.003～0.016, the dielectric loss of the film that comparative example obtains in 10KHz～100KHz frequency rangeBe 0.081～0.02; Growing in 1.0 ° and 5.0 ° cut sth. askew on-chip film and comparative examples grows in common substrateFilm compare, dielectric loss obviously reduces, and under compression stress, dielectric loss can be obviously due to CCTOReduce, grow in suffered compression maximum in 2.5 ° of on-chip pellicular fronts of cutting sth. askew, thereby there is minimum JieElectrical loss. The present invention adopts the substrate of cutting sth. askew of different angles, can effectively reduce dislocation in CCTO film closeDegree, thus dielectric loss reduced, can ensure under the prerequisite of CCTO film high-k effectively reductionThe dielectric loss of film.

Claims (4)

1. a CaCu3Ti4O12The preparation method of film, comprises the following steps:
Step 1, preparation CaCu3Ti4O12Precursor liquid;
Step 2, LaAlO3The cut sth. askew heat treatment of substrate: by LaAlO3The substrate of cutting sth. askew is put into tube furnace, risesTemperature to 800～1000 DEG C and keep 1～6 hour, is cooled to room temperature with stove, what to obtain surface be ledge structureSubstrate;
Step 3, the precursor liquid that adopts the method for spin coating that step 1 is prepared are evenly coated on step 2 after processingTo the surface substrate surface that is ledge structure, dry, obtain the film sample of calcic copper titanium;
The film sample of step 4, calcic copper titanium that step 3 is obtained is heat-treated, then naturally cold with stoveBut to room temperature, obtain CaCu of the present invention3Ti4O12Film.
2. CaCu according to claim 13Ti4O12The preparation method of film, is characterized in that, stepLaAlO described in 23The mis-cut angle of substrate of cutting sth. askew is 1.0 °, 2.5 ° or 5.0 °.
3. CaCu according to claim 13Ti4O12The preparation method of film, is characterized in that, stepDescribed in 1, prepare CaCu3Ti4O12The detailed process of precursor liquid be: respectively by containing calcium salt, mantoquita, titanium saltMixed liquor mixes with water soluble polymer, obtains containing calcium complex mixed liquor, copper-bearing complex mixed liquor, titaniferousComplex compound mixed liquor, then according to containing calcium complex, copper-bearing complex, being 1:3:4 containing the mol ratio of titanium complexRatio, preparation obtains the mixed liquor of calcic copper titanium, as preparation CaCu3Ti4O12The precursor liquid of film.
4. CaCu according to claim 13Ti4O12The preparation method of film, is characterized in that, stepDescribed in 4, heat treated gas atmosphere is oxidizing atmosphere, and heat treatment temperature is 800～1000 DEG C, and heat treatment time is1～6 hour.
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CN107794516A (en) * 2017-10-27 2018-03-13 周燕红 A kind of preparation method of high dielectric constant film
CN109721353A (en) * 2019-03-15 2019-05-07 上海朗研光电科技有限公司 A kind of preparation method of huge dielectric constant CCTO based film material
CN113121221A (en) * 2021-04-22 2021-07-16 郑州轻工业大学 Preparation method of high-dielectric-property calcium copper titanate epitaxial film

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107794516A (en) * 2017-10-27 2018-03-13 周燕红 A kind of preparation method of high dielectric constant film
CN109721353A (en) * 2019-03-15 2019-05-07 上海朗研光电科技有限公司 A kind of preparation method of huge dielectric constant CCTO based film material
CN113121221A (en) * 2021-04-22 2021-07-16 郑州轻工业大学 Preparation method of high-dielectric-property calcium copper titanate epitaxial film
CN113121221B (en) * 2021-04-22 2022-07-19 郑州轻工业大学 Preparation method of high-dielectric-property calcium copper titanate epitaxial film

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