CN109576681B - YDMCO film with low leakage current and preparation method thereof - Google Patents

YDMCO film with low leakage current and preparation method thereof Download PDF

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CN109576681B
CN109576681B CN201811496649.1A CN201811496649A CN109576681B CN 109576681 B CN109576681 B CN 109576681B CN 201811496649 A CN201811496649 A CN 201811496649A CN 109576681 B CN109576681 B CN 109576681B
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谈国强
任茜茜
刘云
薛敏涛
任慧君
夏傲
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Shaanxi University of Science and Technology
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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
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    • C23C18/1295—Process of deposition of the inorganic material with after-treatment of the deposited inorganic material

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Abstract

The invention provides a low-leakage-current YDMCO film and a preparation method thereof, wherein the chemical formula is Y1‑xDyxMn0.5Cr0.5O3Wherein x is more than or equal to 0.1 and less than or equal to 0.5, hexagonal structure and space group is P63cm. Y of the invention1‑xDyxMn0.5Cr0.5O3The film is in YMnO3The A site is doped with rare earth ions, the B site is doped with transition metal ions, and experiments prove that Dy is doped into the middle layer of the double pyramid structure and Cr doping inhibits Mn3+Conversion to Mn2+And Mn4+Finally make Y1‑xDyxMn0.5Cr0.5O3The internal structure of the film is distorted, and the distortion of the hexagonal structure causes the leakage current mechanism of the film to be converted into a single ohmic mechanism from the coexistence of an ohmic mechanism and a space charge mechanism, so that the leakage current density is finally reduced.

Description

YDMCO film with low leakage current and preparation method thereof
Technical Field
The invention belongs to the field of functional materials, and particularly relates to a Y with low leakage current1-xDyxMn0.5Cr0.5O3(abbreviated as YDMCO) film and a preparation method thereof.
Background
With the development and progress of science and technology, various electronic products are developed towards high integration and high complexity, so that the requirement for miniaturization is more and more strict, and therefore, thin film products slowly enter the stage of the electronic products and slowly become an indispensable part of the stage. Meanwhile, modern electronic products are also on the trend of multi-functionalization, so that thin film products made of multiferroic materials are more popular.
Traditional multiferroic material BiFeO3、LuFeO3Most of the materials are perovskite structures or perovskite distorted structures, the multiferroic materials with other structures are less developed, and hexagonal YMnO3The advent of multiferroic materials has made possible other structural multiferroic materials than the perovskite structure. The research finds that the traditional BiFeO3The middle Bi element is easy to volatilize, so that the concentration of oxygen vacancy in the structure is increased, electrons are generated to move, the leakage current density is increased, the performance of the film is reduced, and the service life of the film is shortened. And alsoBiFeO3The plurality of polarization axes cause the film structure to twist or distort towards different directions, thereby causing the performance of the film to change, and finally forming a film product with poor quality. In contrast, the novel YMnO3The composition of the medium substance does not contain volatile elements, so that the film is ensured not to generate more oxygen vacancies due to the volatilization of the substance elements to a certain extent, and the performance of the film is not reduced. Simultaneous YMnO3Single polarization axis in the structure, relative to BiFeO3In terms of structure, the torsion or change of the structure is directional and controllable, and cracks caused by the fact that ferroelectric domains are turned over due to difference are avoided. And its dielectric constant is low, which makes its application in the ferroelectric random access memory with metal-ferroelectric-semiconductor field effect transistor as structure more advantageous.
YMnO3The film is not like BiFeO3The volatile element Bi of the film, but the presence of the valence-variable element Mn also makes the film sample performance worse. And the valence of Mn is more, resulting in YMnO3The valence state of Mn participating in the internal structure is changed under different valence states, so that oxygen vacancy or current carriers in the structure are increased, and finally the density of leakage current in the film sample is increased.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides the YDMCO film with low leakage current and the preparation method thereof, and the leakage current of the obtained film is reduced.
In order to achieve the purpose, the invention adopts the technical scheme that:
a low leakage current YDMCO film with a chemical formula of Y1-xDyxMn0.5Cr0.5O3Wherein x is more than or equal to 0.1 and less than or equal to 0.5, hexagonal structure and space group is P63cm。
Preferably, Y is under the condition of an external electric field of 300kV/cm0.1Dy0.4Mn0.5Cr0.5O3The leakage current density of the film is 0.011A/cm2。
A preparation method of the YDMCO film with low leakage current comprises the following steps,
step 1, dissolving yttrium nitrate, dysprosium nitrate, manganese acetate and chromium nitrate in ethylene glycol monomethyl ether according to a stoichiometric ratio, uniformly stirring, adding acetic anhydride, and continuously stirring until the mixture is uniform to obtain a precursor solution;
step 2, spin-coating the precursor solution on a Si substrate to obtain a wet film, baking the wet film at 170-190 ℃ after glue homogenizing to obtain a dry film, and annealing at 400-500 ℃ to obtain crystalline Y1-xDyxMn0.5Cr0.5O3A film;
step 3, mixing the crystalline state Y1-xDyxMn0.5Cr0.5O3Cooling the film to room temperature, and repeating the step 2 until a crystalline state Y with a preset thickness is obtained1-xDyxMn0.5Cr0.5O3A film;
step 4, the crystalline state Y obtained in step 31-xDyxMn0.5Cr0.5O3Annealing the film at 700-900 ℃ to obtain Y with low leakage current1-xDyxMn0.5Cr0.5O3A film.
Preferably, in the step 1, the volume ratio of the ethylene glycol monomethyl ether to the acetic anhydride is (2.5-3): 1.
Preferably, in the step 2, the spin speed of the spin coating is 2700-3000 r/min, and the spin coating time is 15-20 s.
Preferably, in the step 2, the baking time is 4-6 min.
Preferably, in the step 2, the annealing time is 10-15 min.
Preferably, in the step 4, the annealing time is 80-90 min.
Compared with the prior art, the invention has the beneficial effects that:
y of the invention1-xDyxMn0.5Cr0.5O3The film is in YMnO3The A site is doped with rare earth ions, the B site is doped with transition metal ions, and experiments prove that Dy is doped into the middle layer of the double pyramid structure and Cr doping inhibits Mn3+Conversion to Mn2+And Mn4+Finally make Y1-xDyxMn0.5Cr0.5O3The internal structure of the film is distorted, and the properties of the film sample become stable. The XRD pattern shows that the unit cell parameter c of the film is greatly changed, and the Raman scattering spectrogram shows that the Cr is added3+And Dy3+Respectively enter MnO5And Y3 +The structural layer or Y-Mn bond and Mn-O bond entering the unit cell structure generate the torsion of the bond and the change of the bond angle, and the results all prove that the doping of Dy and Cr causes the hexagonal structure of the film to be distorted, and the distortion of the hexagonal structure causes the leakage current mechanism of the film to be converted into a single ohmic mechanism from the coexistence of an ohmic mechanism and a space charge mechanism, so that the leakage current density is finally changed from 0.039A/cm2The reduction is 0.011A/cm2The leakage current density is greatly reduced.
The invention adopts a sol-gel method to prepare Y1-xDyxMn0.5Cr0.5O3The preparation method of the film is convenient and simple, the chemical reaction can be carried out under the low-temperature condition, the film can be prepared on substrates with different shapes or even irregular shapes, the types of film samples can be directly changed by the proportion of raw materials, and the homogenization of the molecular level can be obtained.
Drawings
FIG. 1 is Y prepared according to the present invention1-xDyxMn0.5Cr0.5O3XRD pattern of the film;
FIG. 2 is Y prepared according to the present invention1-xDyxMn0.5Cr0.5O3Cell parameter variation diagram of the film;
FIG. 3 is Y prepared according to the present invention1-xDyxMn0.5Cr0.5O3A Raman spectrum of the film;
FIG. 4 is Y prepared according to the present invention1-xDyxMn0.5Cr0.5O3A leakage current profile of the film;
FIG. 5 shows Y prepared according to the present invention1-xDyxMn0.5Cr0.5O3And (5) fitting a leakage current mechanism of the film.
Detailed Description
The present invention will now be described in further detail with reference to specific examples, which are intended to be illustrative, but not limiting, of the invention.
The low leakage current YDMCO film has a chemical formula of Y1-xDyxMn0.5Cr0.5O3Wherein x is more than or equal to 0.1 and less than or equal to 0.5, hexagonal structure and space group is P63cm, no other miscellaneous phases appear.
Said Y1-xDyxMn0.5Cr0.5O3The film is pure phase YMnO under the condition of an external electric field of 300kV/cm3Has a leakage current density of 0.039A/cm2，Y0.1Dy0.4Mn0.5Cr0.5O3The leakage current density of the film is 0.011A/cm2The leakage current density of the pure phase film is about 3 times that of the doped film.
Said Y1-xDyxMn0.5Cr0.5O3The preparation method of the film comprises the following steps:
step 1: y (NO) is added according to the molar ratio of (1-x) x:0.5:0.53)3·6H2O、Dy(NO3)3·6H2O、C4H6MnO4·4H2O and Cr (NO)3)3·9H2Dissolving O in ethylene glycol monomethyl ether, stirring uniformly, adding acetic anhydride, and continuously stirring uniformly to obtain a precursor solution;
step 2: spin-coating the precursor solution on a Si substrate to obtain a wet film, baking the wet film at 170-190 ℃ after glue homogenizing to obtain a dry film, and then quickly annealing at 400-500 ℃ to obtain a crystalline film;
and step 3: crystalline state Y1-xDyxMn0.5Cr0.5O3Cooling the film to room temperature, and repeating the step 2 to obtain Y with the required thickness1-xDyxMn0.5Cr0.5O3A film is then annealed at the final temperature of 700-900 ℃ to obtain Y1-xDyxMn0.5Cr0.5O3A film.
In the step 1, the volume ratio of ethylene glycol monomethyl ether to acetic anhydride is (2.5-3) to 1;
in the step 2, the rotating speed of the spin coater is 2700-3000 r/min, and the spin time is 15-20 s;
in the step 2, the baking time of the wet film is 4-6 min, and the annealing time is 10-15 min.
In the step 3, the annealing time is 80-90 min.
Example 1:
1) mixing Y (NO)3)3·6H2O、Dy(NO3)3·6H2O、C4H6MnO4·4H2O and Cr (NO)3)3·9H2Dissolving O in ethylene glycol monomethyl ether at a molar ratio of 0.9:0.1:0.5:0.5, stirring for 1 hr, adding acetic anhydride, and stirring for 1.5 hr to obtain stable Y0.9Dy0.1Mn0.5Cr0.5O3A precursor solution; wherein, Y0.9Dy0.1Mn0.5Cr0.5O3The volume ratio of ethylene glycol monomethyl ether to acetic anhydride in the precursor liquid is 3: 1;
2) standing the precursor solution for 24h, and spin-coating Y on a Si substrate by using a spin-coating method0.9Dy0.1Mn0.5Cr0.5O3Preparing a wet film from the precursor solution, homogenizing the wet film for 20s at 3000r/min, baking the wet film for 5min at 180 ℃ to obtain a dry film, rapidly annealing the dry film for 15min at 450 ℃, cooling to room temperature, and repeating the spin coating-rapid process in the step 2) until the crystalline state Y with the required thickness is prepared0.9Dy0.1Mn0.5Cr0.5O3The film is subjected to final high-temperature annealing at 800 ℃ for 90min to obtain the required Y0.9Dy0.1Mn0.5Cr0.5O3A film.
Example 2:
1) mixing Y (NO)3)3·6H2O、Dy(NO3)3·6H2O、C4H6MnO4·4H2O and Cr (NO)3)3·9H2Dissolving O in ethylene glycol monomethyl ether at a molar ratio of 0.8:0.2:0.5:0.5, stirring for 1 hr, adding acetic anhydride, and stirringStirring for 1.5h to obtain stable Y0.8Dy0.2Mn0.5Cr0.5O3A precursor solution; wherein, Y0.8Dy0.2Mn0.5Cr0.5O3The volume ratio of ethylene glycol monomethyl ether to acetic anhydride in the precursor liquid is 3: 1;
2) standing the precursor solution for 24h, and spin-coating Y on a Si substrate by using a spin-coating method0.8Dy0.2Mn0.5Cr0.5O3Preparing a wet film from the precursor solution, homogenizing the wet film for 20s at 3000r/min, baking the wet film for 5min at 180 ℃ to obtain a dry film, rapidly annealing the dry film for 15min at 450 ℃, cooling to room temperature, and repeating the spin coating-rapid process in the step 2) until the crystalline state Y with the required thickness is prepared0.8Dy0.2Mn0.5Cr0.5O3The film is subjected to final high-temperature annealing at 800 ℃ for 90min to obtain the required Y0.8Dy0.2Mn0.5Cr0.5O3A film.
Example 3:
1) mixing Y (NO)3)3·6H2O、Dy(NO3)3·6H2O、C4H6MnO4·4H2O and Cr (NO)3)3·9H2Dissolving O in ethylene glycol monomethyl ether at a molar ratio of 0.7:0.3:0.5:0.5, stirring for 1 hr, adding acetic anhydride, and stirring for 1.5 hr to obtain stable Y0.7Dy0.3Mn0.5Cr0.5O3A precursor solution; wherein, Y0.7Dy0.3Mn0.5Cr0.5O3The volume ratio of ethylene glycol monomethyl ether to acetic anhydride in the precursor liquid is 3: 1;
2) standing the precursor solution for 24h, and spin-coating Y on a Si substrate by using a spin-coating method0.7Dy0.3Mn0.5Cr0.5O3Preparing a wet film from the precursor solution, homogenizing the wet film for 20s at 3000r/min, baking the wet film for 5min at 180 ℃ to obtain a dry film, rapidly annealing the dry film for 15min at 450 ℃, cooling to room temperature, and repeating the spin coating-rapid process in the step 2) until the crystalline state Y with the required thickness is prepared0.7Dy0.3Mn0.5Cr0.5O3A thin film of a material selected from the group consisting of,and carrying out final high-temperature annealing at 800 ℃ for 90min to obtain the required Y0.7Dy0.3Mn0.5Cr0.5O3A film.
Example 4:
1) mixing Y (NO)3)3·6H2O、Dy(NO3)3·6H2O、C4H6MnO4·4H2O and Cr (NO)3)3·9H2Dissolving O in ethylene glycol monomethyl ether at a molar ratio of 0.6:0.4:0.5:0.5, stirring for 1 hr, adding acetic anhydride, and stirring for 1.5 hr to obtain stable Y0.6Dy0.4Mn0.5Cr0.5O3A precursor solution; wherein, Y0.6Dy0.4Mn0.5Cr0.5O3The volume ratio of ethylene glycol monomethyl ether to acetic anhydride in the precursor liquid is 3: 1;
2) standing the precursor solution for 24h, and spin-coating Y on a Si substrate by using a spin-coating method0.6Dy0.4Mn0.5Cr0.5O3Preparing a wet film from the precursor solution, homogenizing the wet film for 20s at 3000r/min, baking the wet film for 5min at 180 ℃ to obtain a dry film, rapidly annealing the dry film for 15min at 450 ℃, cooling to room temperature, and repeating the spin coating-rapid process in the step 2) until the crystalline state Y with the required thickness is prepared0.6Dy0.4Mn0.5Cr0.5O3The film is subjected to final high-temperature annealing at 800 ℃ for 90min to obtain the required Y0.6Dy0.4Mn0.5Cr0.5O3A film.
Example 5:
1) mixing Y (NO)3)3·6H2O、Dy(NO3)3·6H2O、C4H6MnO4·4H2O and Cr (NO)3)3·9H2Dissolving O in ethylene glycol monomethyl ether at a molar ratio of 0.5:0.5:0.5:0.5, stirring for 1 hr, adding acetic anhydride, and stirring for 1.5 hr to obtain stable Y0.5Dy0.5Mn0.5Cr0.5O3A precursor solution; wherein, Y0.5Dy0.5Mn0.5Cr0.5O3Ethylene glycol methyl ether and vinegar in the precursor liquidThe volume ratio of the acid anhydride is 3: 1;
2) standing the precursor solution for 24h, and spin-coating Y on a Si substrate by using a spin-coating method0.5Dy0.5Mn0.5Cr0.5O3Preparing a wet film from the precursor solution, homogenizing the wet film for 20s at 3000r/min, baking the wet film for 5min at 180 ℃ to obtain a dry film, rapidly annealing the dry film for 15min at 450 ℃, cooling to room temperature, and repeating the spin coating-rapid process in the step 2) until the crystalline state Y with the required thickness is prepared0.5Dy0.5Mn0.5Cr0.5O3The film is subjected to final high-temperature annealing at 800 ℃ for 90min to obtain the required Y0.5Dy0.5Mn0.5Cr0.5O3A film.
Example 6:
1) mixing Y (NO)3)3·6H2O、Dy(NO3)3·6H2O、C4H6MnO4·4H2O and Cr (NO)3)3·9H2Dissolving O in ethylene glycol monomethyl ether at a molar ratio of 0.5:0.5:0.5:0.5, stirring for 1 hr, adding acetic anhydride, and stirring for 1.5 hr to obtain stable Y0.5Dy0.5Mn0.5Cr0.5O3A precursor solution; wherein, Y0.5Dy0.5Mn0.5Cr0.5O3The volume ratio of ethylene glycol monomethyl ether to acetic anhydride in the precursor liquid is 2.5: 1;
2) standing the precursor solution for 24h, and spin-coating Y on a Si substrate by using a spin-coating method0.5Dy0.5Mn0.5Cr0.5O3Preparing a wet film from the precursor solution, homogenizing the wet film for 20s at 2700r/min, baking the wet film for 6min at 170 ℃ to obtain a dry film, rapidly annealing the dry film for 15min at 450 ℃, cooling to room temperature, and repeating the spin coating-rapid process in the step 2) until the crystalline state Y with the required thickness is prepared0.5Dy0.5Mn0.5Cr0.5O3The film is subjected to final high-temperature annealing at 800 ℃ for 85min to obtain the required Y0.5Dy0.5Mn0.5Cr0.5O3A film.
Example 7:
1) mixing Y (NO)3)3·6H2O、Dy(NO3)3·6H2O、C4H6MnO4·4H2O and Cr (NO)3)3·9H2Dissolving O in ethylene glycol monomethyl ether at a molar ratio of 0.5:0.5:0.5:0.5, stirring for 1 hr, adding acetic anhydride, and stirring for 1.5 hr to obtain stable Y0.5Dy0.5Mn0.5Cr0.5O3A precursor solution; wherein, Y0.5Dy0.5Mn0.5Cr0.5O3The volume ratio of ethylene glycol monomethyl ether to acetic anhydride in the precursor liquid is 2.7: 1;
2) standing the precursor solution for 24h, and spin-coating Y on a Si substrate by using a spin-coating method0.5Dy0.5Mn0.5Cr0.5O3Preparing a wet film from the precursor solution, homogenizing the wet film for 18s at 2800r/min, baking the wet film for 4min at 190 ℃ to obtain a dry film, rapidly annealing the dry film for 14min at 450 ℃, cooling to room temperature, and repeating the spin coating-rapid process in the step 2) until the crystalline Y with the required thickness is prepared0.5Dy0.5Mn0.5Cr0.5O3The film is subjected to final high-temperature annealing at 800 ℃ for 90min to obtain the required Y0.5Dy0.5Mn0.5Cr0.5O3A film.
Example 8:
1) mixing Y (NO)3)3·6H2O、Dy(NO3)3·6H2O、C4H6MnO4·4H2O and Cr (NO)3)3·9H2Dissolving O in ethylene glycol monomethyl ether at a molar ratio of 0.5:0.5:0.5:0.5, stirring for 1 hr, adding acetic anhydride, and stirring for 1.5 hr to obtain stable Y0.5Dy0.5Mn0.5Cr0.5O3A precursor solution; wherein, Y0.5Dy0.5Mn0.5Cr0.5O3The volume ratio of ethylene glycol monomethyl ether to acetic anhydride in the precursor liquid is 3: 1;
2) standing the precursor solution for 24h, and spin-coating Y on a Si substrate by using a spin-coating method0.5Dy0.5Mn0.5Cr0.5O3Preparing wet film from the precursor solution, wettingHomogenizing the film at 2900r/min for 16s, baking the wet film at 180 deg.C for 5min to obtain dry film, rapidly annealing the dry film at 400 deg.C for 15min, cooling to room temperature, and repeating the spin-coating-rapid process in step 2) until crystalline Y with required thickness is prepared0.5Dy0.5Mn0.5Cr0.5O3The film is subjected to final high-temperature annealing at 800 ℃ for 90min to obtain the required Y0.5Dy0.5Mn0.5Cr0.5O3A film.
Example 9:
1) mixing Y (NO)3)3·6H2O、Dy(NO3)3·6H2O、C4H6MnO4·4H2O and Cr (NO)3)3·9H2Dissolving O in ethylene glycol monomethyl ether at a molar ratio of 0.5:0.5:0.5:0.5, stirring for 1 hr, adding acetic anhydride, and stirring for 1.5 hr to obtain stable Y0.5Dy0.5Mn0.5Cr0.5O3A precursor solution; wherein, Y0.5Dy0.5Mn0.5Cr0.5O3The volume ratio of ethylene glycol monomethyl ether to acetic anhydride in the precursor liquid is 3: 1;
2) standing the precursor solution for 24h, and spin-coating Y on a Si substrate by using a spin-coating method0.5Dy0.5Mn0.5Cr0.5O3Preparing a wet film from the precursor solution, homogenizing the wet film for 15s at 3000r/min, baking the wet film for 5min at 180 ℃ to obtain a dry film, rapidly annealing the dry film for 12min at 500 ℃, cooling to room temperature, and repeating the spin coating-rapid process in the step 2) until the crystalline state Y with the required thickness is prepared0.5Dy0.5Mn0.5Cr0.5O3The film is subjected to final high-temperature annealing at 800 ℃ for 90min to obtain the required Y0.5Dy0.5Mn0.5Cr0.5O3A film.
Example 10:
1) mixing Y (NO)3)3·6H2O、Dy(NO3)3·6H2O、C4H6MnO4·4H2O and Cr (NO)3)3·9H2O in molar ratio of 05:0.5:0.5:0.5 dissolving in ethylene glycol monomethyl ether, stirring for 1h, adding acetic anhydride, stirring for 1.5h to obtain stable Y0.5Dy0.5Mn0.5Cr0.5O3A precursor solution; wherein, Y0.5Dy0.5Mn0.5Cr0.5O3The volume ratio of ethylene glycol monomethyl ether to acetic anhydride in the precursor liquid is 3: 1;
2) standing the precursor solution for 24h, and spin-coating Y on a Si substrate by using a spin-coating method0.5Dy0.5Mn0.5Cr0.5O3Preparing a wet film from the precursor solution, homogenizing the wet film for 20s at 3000r/min, baking the wet film for 5min at 180 ℃ to obtain a dry film, rapidly annealing the dry film for 10min at 450 ℃, cooling to room temperature, and repeating the spin coating-rapid process in the step 2) until the crystalline state Y with the required thickness is prepared0.5Dy0.5Mn0.5Cr0.5O3The film is subjected to final high-temperature annealing at 700 ℃ for 90min to obtain the required Y0.5Dy0.5Mn0.5Cr0.5O3A film.
Example 11:
1) mixing Y (NO)3)3·6H2O、Dy(NO3)3·6H2O、C4H6MnO4·4H2O and Cr (NO)3)3·9H2Dissolving O in ethylene glycol monomethyl ether at a molar ratio of 0.5:0.5:0.5:0.5, stirring for 1 hr, adding acetic anhydride, and stirring for 1.5 hr to obtain stable Y0.5Dy0.5Mn0.5Cr0.5O3A precursor solution; wherein, Y0.5Dy0.5Mn0.5Cr0.5O3The volume ratio of ethylene glycol monomethyl ether to acetic anhydride in the precursor liquid is 3: 1;
2) standing the precursor solution for 24h, and spin-coating Y on a Si substrate by using a spin-coating method0.5Dy0.5Mn0.5Cr0.5O3Preparing a wet film from the precursor solution, homogenizing the wet film for 20s at 3000r/min, baking the wet film for 5min at 180 ℃ to obtain a dry film, rapidly annealing the dry film for 15min at 450 ℃, cooling to room temperature, and repeating the spin coating-rapid process in the step 2) until the crystalline state Y with the required thickness is prepared0.5Dy0.5Mn0.5Cr0.5O3Carrying out final high-temperature annealing at 900 ℃ for 80min to obtain the required Y0.5Dy0.5Mn0.5Cr0.5O3A film.
Comparative example 1:
1) mixing Y (NO)3)3·6H2O and C4H6MnO4·4H2Dissolving O in ethylene glycol monomethyl ether at a molar ratio of 1:1, stirring for 1h, adding acetic anhydride, and stirring for 1.5h to obtain stable YMnO3A precursor solution; wherein, YMnO3The volume ratio of ethylene glycol monomethyl ether to acetic anhydride in the precursor liquid is 3: 1;
2) standing the precursor solution for 24h, and spin-coating YMnO on a Si substrate by using a spin-coating method3Preparing a wet film from the precursor solution, homogenizing the wet film for 20s at 3000r/min, baking the wet film for 5min at 180 ℃ to obtain a dry film, rapidly annealing the dry film for 15min at 450 ℃, cooling to room temperature, and repeating the spin coating-rapid process in the step 2) until the crystalline YMnO with the required thickness is prepared3The film is finally annealed at 800 ℃ to obtain the required YMnO3A film.
The phase compositions and structures of the films obtained in examples 1 to 5 and comparative example 1 were measured by XRD, and the results are shown in FIG. 1, Y prepared by sol-gel method1-xDyxMn0.5Cr0.5O3Cell parameters of the film were varied as shown in FIG. 2; determination of Y from examples 1 to 5 and comparative example 1 by Raman Scattering Spectroscopy1-xDyxMn0.5Cr0.5O3The chemical bond state and the film structure of the film, and the measurement results are shown in FIG. 3; detection of Y with Agilent B2901A1-xDyxMn0.5Cr0.5O3The leakage performance of the film is shown in FIG. 4; for Y1-xDyxMn0.5Cr0.5O3The leakage current of the thin film was subjected to piecewise fitting, and the fitting result is shown in fig. 5.
FIG. 1 shows Y obtained by the present invention1-xDyxMn0.5Cr0.5O3Of filmsAn XRD pattern, compared with a standard card of PDF25-1079, shows that the (112), (104), (202), (113), (114) and (215) crystal planes at diffraction angles 2 theta of 33.23 degrees, 36.10 degrees, 37.40 degrees, 38.21 degrees, 43.30 degrees and 62.35 degrees correspond to the standard card. Thereby determining Y1-xDyxMn0.5Cr0.5O3The film has a hexagonal structure and space group P63cm, no generation of hetero-phase.
FIG. 2 is Y1-xDyxMn0.5Cr0.5O3Film with Dy3+Variation of doping amount as seen from the graph of variation of cell parameters, when the doping amount x is 0.2, the cell parameters change, and Y is1-xDyxMn0.5Cr0.5O3The cell parameter c of the film varied greatly and differed from comparative example 1 by approximately
Figure BDA0001897051360000101
The internal structure of the film was distorted, which was further demonstrated.
FIG. 3 is Y1-xDyxMn0.5Cr0.5O3The Raman scattering spectrum of the film showed that 7 vibration modes, each 175cm in E2 mode, were found in FIG. 2-1And A1146cm of mode-1、394cm-1、495cm-1、518cm-1、618cm-1And 685cm-1Raman peak of (a). The E2 mode is associated with a Mn-O bond, A1The mode is related to Y-O bond and Mn-O bond. The raman vibration peak at x ═ 0.1, the doping amount was found to be more pronounced than that of the other films, 685cm-1The Raman peak shifts to a high frequency and gradually widens due to the addition of Cr3+And Y3+Respectively enter MnO5And Y3+The structural layer or the Y-Mn bond and the Mn-O bond entering the unit cell structure distort the hexagonal structure of the film, generate the twist of the bond and the change of the bond angle and finally lead to the shift and the broadening of the Raman peak.
FIG. 4 is a pure phase YMnO3And Y0.1Dy0.4Mn0.5Cr0.5O3Leakage of electricity from thin filmFlow diagram, in which pure phase YMnO is found under the condition of an applied electric field of 300kV/cm3Has a leakage current density of 0.039A/cm2，Y0.1Dy0.4Mn0.5Cr0.5O3The leakage current density of the film is 0.011A/cm2The leakage current density of the pure phase film is about 3 times that of the doped film.
FIG. 5 is a pure phase YMnO3And Y0.1Dy0.4Mn0.5Cr0.5O3The sectional fitting graph of the leakage current of the film can obtain the fitted pure phase YMnO under the 20V applied electric field3The film slope is 1.03 for s1 and 1.31 for s2, and the leakage current mechanism is gradually converted from the ohmic mechanism to the space charge mechanism. Y is0.1Dy0.4Mn0.5Cr0.5O3The slope of the film is 1.61, and the leakage current mechanism is an ohmic mechanism. As can be seen from fig. 3, the change of the leakage current mechanism affects the magnitude of the leakage current.
The above-described details are provided for the purpose of describing particular preferred embodiments of the present invention in more detail, and it is not intended to limit the invention to all or the only embodiments, and any equivalents of the technical solutions of the present invention which are obvious to those skilled in the art from reading the present specification are covered by the claims of the present invention.

Claims (4)

1. A preparation method of YDMCO film with low leakage current is characterized by comprising the following steps,
step 1, according to Y1-xDyxMn0.5Cr0.5O3Dissolving yttrium nitrate, dysprosium nitrate, manganese acetate and chromium nitrate in ethylene glycol monomethyl ether, stirring uniformly, adding acetic anhydride, and continuously stirring uniformly to obtain a precursor solution; wherein x is more than or equal to 0.1 and less than or equal to 0.5;
step 2, spin-coating the precursor solution on a Si substrate to obtain a wet film, baking the wet film at 170-190 ℃ after glue homogenizing to obtain a dry film, and annealing at 400-500 ℃ to obtain crystalline Y1-xDyxMn0.5Cr0.5O3A film;
step 3, mixing the crystalline state Y1-xDyxMn0.5Cr0.5O3Cooling the film to room temperature, and repeating the step 2 until a crystalline state Y with a preset thickness is obtained1-xDyxMn0.5Cr0.5O3A film;
step 4, the crystalline state Y obtained in step 31-xDyxMn0.5Cr0.5O3Annealing the film at 700-900 ℃ to obtain Y with low leakage current1-xDyxMn0.5Cr0.5O3A film;
in the step 2, the spin rate of the spin coating is 2700-3000 r/min, and the spin coating time is 15-20 s;
in the step 2, the baking time is 4-6 min;
in the step 2, the annealing time is 10-15 min;
in the step 4, the annealing time is 80-90 min.
2. The method for preparing the YDMCO film with low leakage current according to claim 1, wherein in the step 1, the volume ratio of ethylene glycol monomethyl ether to acetic anhydride is (2.5-3): 1.
3. The YDMCO film with low leakage current prepared by the method according to claim 1, wherein the chemical formula is Y1-xDyxMn0.5Cr0.5O3Hexagonal structure, space group P63cm。
4. The YDMCO film with low leakage current according to claim 3, characterized in that Y is applied under the condition of an applied electric field of 300kV/cm0.1Dy0.4Mn0.5Cr0.5O3The leakage current density of the film is 0.011A/cm2。
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