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CN101580391A - Method for preparing manganese-stabilized zirconia film - Google Patents

Method for preparing manganese-stabilized zirconia film Download PDF

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Publication number
CN101580391A
CN101580391A CNA2009100230661A CN200910023066A CN101580391A CN 101580391 A CN101580391 A CN 101580391A CN A2009100230661 A CNA2009100230661 A CN A2009100230661A CN 200910023066 A CN200910023066 A CN 200910023066A CN 101580391 A CN101580391 A CN 101580391A
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stabilized zirconia
manganese
film
target
substrate
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卢亚锋
白利锋
冯建情
李成山
闫果
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Northwest Institute for Non Ferrous Metal Research
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Northwest Institute for Non Ferrous Metal Research
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Abstract

本发明公开了一种锰稳定氧化锆薄膜的制备方法，制备过程为：以金属氧化物ZrO2粉末和MnO2粉末为原料，按Zr0.75Mn0.25O2中阳离子的摩尔比为3∶1称量，混合、研磨、烧结；再次研磨、压片后重复烧结，并将烧结样品打磨后得到靶材，在一定的衬底温度、氩气分压、靶－衬距离下，入射到靶材表面的脉冲激光剥蚀靶体，形成羽辉后将掺杂氧化锆沉积到衬底钇稳定的氧化锆单晶基片上，制得锰稳定氧化锆薄膜。本发明工艺简单，所制备的锰稳定氧化锆薄膜具有很好的c轴织构，表面光滑致密，锰稳定氧化锆薄膜与单晶衬底之间具有原子级的锐利界面。The invention discloses a method for preparing a manganese-stabilized zirconia film . The preparation process is as follows: metal oxide ZrO2 powder and MnO2 powder are used as raw materials, and the molar ratio of cations in Zr0.75Mn0.25O2 is 3:1. measuring, mixing, grinding, and sintering; regrinding, tableting, and repeated sintering, and the sintered sample was polished to obtain a target, and the target was incident on the surface of the target at a certain substrate temperature, argon partial pressure, and target-substrate distance. The target body was ablated by the pulsed laser, and after the plume was formed, the doped zirconia was deposited on the substrate yttrium-stabilized zirconia single crystal substrate, and the manganese-stabilized zirconia thin film was prepared. The process of the invention is simple, and the prepared manganese stabilized zirconia film has good c-axis texture, smooth and compact surface, and the manganese stabilized zirconia film and the single crystal substrate have a sharp interface at the atomic level.

Description

A kind of preparation method of manganese-stabilized zirconia film
Technical field
The present invention relates to a kind of preparation method of manganese-stabilized zirconia film, be specifically related to the manganese-stabilized zirconia Zr that has the widespread use potentiality in the fields such as a kind of gate medium, magneticthin film, conductor of high-temperature superconductor coat in oxide semiconductor devices 0.75Mn 0.25O 2The preparation method of film.
Background technology
Zirconium white (ZrO 2) the material potentiality that in oxygen probe, high-temperature fuel cell, catalysis technique and light guide, have a wide range of applications.Zirconium white (ZrO 2) also be a kind of high temperature resistant structure ceramics, fusing point is up to 2973K.Under atmospheric environment, zirconium white exists three kinds of paramorphs, i.e. oblique system (m-ZrO 2), tetragonal system (t-ZrO 2) and isometric system (c-ZrO 2).Pure ZrO 2In the process of cooling behind sintering the martensitic transformation that the monocline phase is arrived in the four directions mutually can take place, be attended by volume change simultaneously, the material that causes preparing ftractures, and has limited the application of zirconia material on engineering.
Exploitation zirconium white (ZrO 2) thin-film material is significant for fields such as the gate medium in the oxide semiconductor devices, magneticthin film, conductor of high-temperature superconductor coat.Use at the grid material in the semi-conductor, Theoretical Calculation shows, the specific inductivity of four directions phase can be up to 47, therefore stablize the important directions that the high temperature four directions becomes zirconia material research mutually, and prepare the mutually single-orientated film in four directions even monocrystal thin films just becomes the focus that novel grid material is studied in the semi-conductor.Generally, pure zirconium white (ZrO 2) film is difficult for presenting single cubic phase, a small amount of monocline is met association in zirconia film, and second phase oxide can occur at the interface in substrate/film.Introduce magnetic element and can obtain ferromagnetic semiconductor in transition metal oxide, this material will greatly influence following information technology.The application of these ferromagnetic semiconductor materials at first depends on the character of their films, yet the research of the adulterated zirconia film of magnetic element rarely has report.In conductor of high-temperature superconductor coat, the keying action that is in the buffer layer between metal base band and the superconducting layer is chemical barrier and texture transmission.Stability Analysis of Structures and structure matching are to select the important evidence of buffer layer.In stabilizing zirconia (hafnium) material, only there is the stable zirconium white of yttrium (YSZ) film to be used in the coating conductor buffer layer, yet utilize the YSZ of magnetron sputtering deposition can not be applied in the Seed Layer of buffer layer, because along with the increase of YSZ film thickness, the YSZ film ftractures easily.Therefore, exploring novel cushioning layer material and technology of preparing thereof also is one of the striving direction in present conductor of high-temperature superconductor coat field.
Summary of the invention
Technical problem to be solved by this invention is the deficiency that exists at prior art, proposes a kind of preparation method of manganese-stabilized zirconia film, and the stablizer that liptinite material zirconium white is adopted is MnO 2, preparing the method that manganese-stabilized zirconia film adopts is pulsed laser deposition.Present method can overcome the problem that monocline that prior art exists during zirconia film in preparation and high temperature are mixedly mutually deposited, substrate/film is prone to second phase oxide at the interface, and preparation technology simply reaches good reproducibility, the sharp keen interface that has atom level between the manganese-stabilized zirconia film of this method preparation and the single crystalline substrate.
For solving the problems of the technologies described above, the technical solution used in the present invention is: a kind of preparation method of manganese-stabilized zirconia film is characterized in that preparation process is:
(1) according to Zr 0.75Mn 0.25O 2In the mol ratio of Zr: Mn be to take by weighing metal oxide ZrO at 3: 1 2Powder and MnO 2Powder takes out after constant temperature under 1400 ℃ of temperature is handled 12-24 hour behind the mixed grinding;
(2) carefully grind again, mix fully, on tabletting machine, mixed powder is pressed into disk with the converted steel mould;
(3) disk in the step (2) is placed in the corundum crucible, sintering in carborunbum tube heating element tube type high-temperature furnace in 1400 ℃ of sintering temperature 12-24 hours, cools to room temperature with the furnace then in argon gas atmosphere, obtain corresponding stabilizing zirconia sample;
(4) the stabilizing zirconia sample surfaces in the step (3) is polished be prepared into target;
(5) with sediment chamber's forvacuum, with the YSZ single-crystal substrate after cleaning as substrate, in argon gas atmosphere, pressure is under the deposition pressure and 800-900 ℃ of underlayer temperature of 5-10Pa, with energy is that 550mJ and frequency are that the pulse laser of 5-10Hz degrades described in the step (4) target 15-30 minute to obtain film, and in a normal atmosphere argon gas, described film is cooled to room temperature, promptly make manganese-stabilized zirconia film, wherein, described YSZ is meant the zirconium white that yttrium is stable.
The pressure of tabletting machine is 10Mpa described in the above-mentioned steps (2).
The vacuum tightness of sediment chamber is 2 * 10 described in the above-mentioned steps (5) -4Pa.
The present invention compared with prior art has the following advantages: the present invention prepares under higher underlayer temperature and argon gas atmosphere condition, help eliminating the formation of the substrate/film interface amorphous layer and second phase oxide, the manganese-stabilized zirconia film of preparing has good c axle texture and even curface; Present invention can be implemented in and prepare manganese-stabilized zirconia film in the broad underlayer temperature scope fast.
Below by embodiment, the present invention is described in further detail.
Embodiment
Embodiment 1
With ZrO 2Powder and MnO 2Powder is a raw material, mol ratio by Zr: Mn is weighing in 3: 1, mixing, grinding 2h, after handling 12-24 hour, takes out constant temperature under 1400 ℃ of temperature, carefully grind 2h again, mix fully, weighing 5g portion is used the converted steel mould on tabletting machine, adopt the pressure of 10MPa to be pressed into diameter and be 20mm, thickly be the disk shape sample of 2mm.Sample is placed on corundum crucible and is placed in the carborunbum tube heating element tube type high-temperature furnace, under ar gas environment, cools to room temperature with the furnace after 1400 ℃ of sintering temperature 12-24 hours, has promptly made Zr 0.75Mn 0.25O 2The stabilizing zirconia bulk will make target after the bulk polishing.Utilize pulsed laser deposition technique to prepare manganese-stabilized zirconia film then, the laser apparatus that uses in the experiment is the COMPex205 type KrF excimer laser that German Lambda Physik company produces, optical maser wavelength is 248nm, pulse width 25ns, pulsed laser energy is 550mJ, pulse-repetition is 5-10Hz, and target-lining distance is 60-65mm, incides target material surface with miter angle after the laser line focus.Selecting single-sided polishing monocrystalline YSZ (zirconium white that yttrium is stable) is substrate, puts into the sediment chamber after the cleaning.Vacuum is 2 * 10 at the bottom of the back of the body of sediment chamber -4Pa, the work Ar Pressure is 5-10Pa, 800 ℃ of underlayer temperatures.Sample slow cooling in 1 normal atmosphere argon gas atmosphere has promptly made and has had the sharp keen manganese-stabilized zirconia film of good c axle texture and interface to room temperature behind the deposition 15-30min.
Embodiment 2
With ZrO 2Powder and MnO 2Powder is a raw material, mol ratio by Zr: Mn is weighing in 3: 1, mixing, grinding 2h, after handling 12-24 hour, takes out constant temperature under 1400 ℃ of temperature, carefully grind 2h again, mix fully, weighing 5g portion is used the converted steel mould on tabletting machine, adopt the pressure of 10MPa to be pressed into diameter and be 20mm, thickly be the disk shape sample of 2mm.Sample is placed on corundum crucible and is placed in the carborunbum tube heating element tube type high-temperature furnace, under ar gas environment, cools to room temperature with the furnace after 1400 ℃ of sintering temperature 12-24 hours, has promptly made Zr 0.75Mn 0.25O 2The stabilizing zirconia bulk will make target after the bulk polishing.Utilize pulsed laser deposition technique to prepare manganese-stabilized zirconia film then, the laser apparatus that uses in the experiment is the COMPex205 type KrF excimer laser that German Lambda Physik company produces, optical maser wavelength is 248nm, pulse width 25ns, pulsed laser energy is 550mJ, pulse-repetition is 5-10Hz, and target-lining distance is 60-65mm, incides target material surface with miter angle after the laser line focus.Selecting single-sided polishing monocrystalline YSZ (zirconium white that yttrium is stable) is substrate, puts into the sediment chamber after the cleaning.Vacuum is 2 * 10 at the bottom of the back of the body of sediment chamber -4Pa, the work Ar Pressure is 5-10Pa, 850 ℃ of underlayer temperatures.Sample slow cooling in 1 normal atmosphere argon gas atmosphere has promptly made and has had the sharp keen manganese-stabilized zirconia film of good c axle texture and interface to room temperature behind the deposition 15-30min.
Embodiment 3
With ZrO 2Powder and MnO 2Powder is a raw material, mol ratio by Zr: Mn is weighing in 3: 1, mixing, grinding 2h, after handling 12-24 hour, takes out constant temperature under 1400 ℃ of temperature, carefully grind 2h again, mix fully, weighing 5g portion is used the converted steel mould on tabletting machine, adopt the pressure of 10MPa to be pressed into diameter and be 20mm, thickly be the disk shape sample of 2mm.Sample is placed on corundum crucible and is placed in the carborunbum tube heating element tube type high-temperature furnace, under ar gas environment, cools to room temperature with the furnace after 1400 ℃ of sintering temperature 12-24 hours, has promptly made Zr 0.75Mn 0.25O 2The stabilizing zirconia bulk will make target after the bulk polishing.Utilize pulsed laser deposition technique to prepare manganese-stabilized zirconia film then, the laser apparatus that uses in the experiment is the COMPex205 type KrF excimer laser that German Lambda Physik company produces, optical maser wavelength is 248nm, pulse width 25ns, pulsed laser energy is 550mJ, pulse-repetition is 5-10Hz, and target-lining distance is 60-65mm, incides target material surface with miter angle after the laser line focus.Selecting single-sided polishing monocrystalline YSZ (zirconium white that yttrium is stable) is substrate, puts into the sediment chamber after the cleaning.Vacuum is 2 * 10 at the bottom of the back of the body of sediment chamber -4Pa, the work Ar Pressure is 5-10Pa, 900 ℃ of underlayer temperatures.Sample slow cooling in 1 normal atmosphere argon gas atmosphere has promptly made and has had the sharp keen manganese-stabilized zirconia film of good c axle texture and interface to room temperature behind the deposition 15-30min.
The manganese-stabilized zirconia film that above example makes shows that through X-ray diffraction analysis these films all have good c-axis texture, and transmission electron microscope (TEM) is observed and shown these manganese-stabilized zirconia film densifications, and the sharp keen interface with atom level.

Claims (3)

1.一种锰稳定氧化锆薄膜的制备方法，其特征在于制备过程为：1. A preparation method for manganese stabilized zirconia film, characterized in that the preparation process is: (1)按照Zr0.75Mn0.25O2中Zr∶Mn的摩尔比为3∶1称取金属氧化物ZrO2粉末和MnO2粉末，混合研磨后在1400℃温度下恒温处理12-24小时后取出；(1) Weigh the metal oxide ZrO 2 powder and MnO 2 powder according to the molar ratio of Zr:Mn in Zr 0.75 Mn 0.25 O 2 is 3:1, mix and grind them, and treat them at a temperature of 1400°C for 12-24 hours before taking them out ; (2)再仔细研磨，混合充分，在压片机上用硬质钢模具将混合粉末压制成圆片；(2) Grind carefully, mix well, and press the mixed powder into discs with a hard steel mold on the tablet machine; (3)将步骤(2)中的圆片放在刚玉坩埚里，在硅碳管发热体管式高温炉内烧结，在氩气气氛中于1400℃温度下烧结12-24小时，然后随炉冷却至室温，得到相应的稳定氧化锆样品；(3) Put the wafer in step (2) in a corundum crucible, sinter it in a silicon carbon tube heating element tubular high-temperature furnace, and sinter it at 1400°C for 12-24 hours in an argon atmosphere, and then follow the furnace Cool to room temperature to obtain the corresponding stabilized zirconia sample; (4)对步骤(3)中的稳定氧化锆样品表面进行打磨制备成靶材；(4) grinding the surface of the stabilized zirconia sample in step (3) to prepare a target; (5)将沉积室预抽真空，以清洗后的YSZ单晶基片作为衬底，在氩气气氛中、压力为5-10Pa的沉积气压和800-900℃衬底温度下，用能量为550mJ和频率为5-10Hz的脉冲激光剥蚀步骤(4)中所述靶材15-30分钟以获得薄膜，并在一个大气压氩气中将所述薄膜冷却至室温，即制得锰稳定氧化锆薄膜，其中，所述YSZ是指钇稳定的氧化锆。(5) Pre-evacuate the deposition chamber, use the cleaned YSZ single crystal substrate as the substrate, and use energy of 550mJ and a frequency of 5-10Hz pulsed laser ablation of the target in step (4) for 15-30 minutes to obtain a film, and cooling the film to room temperature in an atmosphere of argon to produce manganese-stabilized zirconia The thin film, wherein said YSZ refers to yttrium stabilized zirconia. 2.按照权利要求1所述的一种锰稳定氧化锆薄膜的制备方法，其特征在于，步骤(2)中所述压片机的压力为10Mpa。2. according to the preparation method of a kind of manganese-stabilized zirconia film according to claim 1, it is characterized in that, the pressure of tablet press described in step (2) is 10Mpa. 3.按照权利要求1所述的一种锰稳定氧化锆薄膜的制备方法，其特征在于，步骤(5)中所述沉积室的真空度为2×10-4Pa。3 . The method for preparing a manganese-stabilized zirconia thin film according to claim 1 , wherein the vacuum degree of the deposition chamber in step (5) is 2×10 −4 Pa. 4 .
CNA2009100230661A 2009-06-26 2009-06-26 Method for preparing manganese-stabilized zirconia film Pending CN101580391A (en)

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102167586A (en) * 2011-01-20 2011-08-31 中南大学 Low-temperature activated sintered 8YSZ-based ceramic and preparation method thereof
CN103936415A (en) * 2014-03-17 2014-07-23 内蒙古科技大学 Stable zirconia ceramic target material for electron beam physic vapor deposition, and its preparation method
CN104212450A (en) * 2013-05-29 2014-12-17 海洋王照明科技股份有限公司 Luminescent film, preparation method and application thereof
CN110256070A (en) * 2019-07-31 2019-09-20 三祥新材股份有限公司 A kind of preparation method of zirconia film material
CN110804761A (en) * 2019-12-09 2020-02-18 湘潭大学 A kind of preparation method of different orientation single variant yttria stabilized zirconia epitaxial film
CN117144294A (en) * 2023-10-30 2023-12-01 华南理工大学 High dielectric constant calcium stabilized zirconia film and preparation method thereof

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102167586A (en) * 2011-01-20 2011-08-31 中南大学 Low-temperature activated sintered 8YSZ-based ceramic and preparation method thereof
CN104212450A (en) * 2013-05-29 2014-12-17 海洋王照明科技股份有限公司 Luminescent film, preparation method and application thereof
CN103936415A (en) * 2014-03-17 2014-07-23 内蒙古科技大学 Stable zirconia ceramic target material for electron beam physic vapor deposition, and its preparation method
CN110256070A (en) * 2019-07-31 2019-09-20 三祥新材股份有限公司 A kind of preparation method of zirconia film material
CN110256070B (en) * 2019-07-31 2022-05-17 三祥新材股份有限公司 Preparation method of zirconia film material
CN110804761A (en) * 2019-12-09 2020-02-18 湘潭大学 A kind of preparation method of different orientation single variant yttria stabilized zirconia epitaxial film
CN117144294A (en) * 2023-10-30 2023-12-01 华南理工大学 High dielectric constant calcium stabilized zirconia film and preparation method thereof
CN117144294B (en) * 2023-10-30 2024-02-20 华南理工大学 High dielectric constant calcium stabilized zirconia film and preparation method thereof

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