CN100519824C - Preparation method lowering annealing temperature of spinel ferrite thin film material - Google Patents

Preparation method lowering annealing temperature of spinel ferrite thin film material Download PDF

Info

Publication number
CN100519824C
CN100519824C CNB2007100503481A CN200710050348A CN100519824C CN 100519824 C CN100519824 C CN 100519824C CN B2007100503481 A CNB2007100503481 A CN B2007100503481A CN 200710050348 A CN200710050348 A CN 200710050348A CN 100519824 C CN100519824 C CN 100519824C
Authority
CN
China
Prior art keywords
thin film
spinel
film
preparation
ferrite
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
CNB2007100503481A
Other languages
Chinese (zh)
Other versions
CN101230446A (en
Inventor
钟智勇
张怀武
荆玉兰
刘爽
唐晓莉
苏桦
贾利军
金沈贤
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
University of Electronic Science and Technology of China
Original Assignee
University of Electronic Science and Technology of China
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by University of Electronic Science and Technology of China filed Critical University of Electronic Science and Technology of China
Priority to CNB2007100503481A priority Critical patent/CN100519824C/en
Publication of CN101230446A publication Critical patent/CN101230446A/en
Application granted granted Critical
Publication of CN100519824C publication Critical patent/CN100519824C/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Abstract

The invention relates to a preparing method of reducing the annealing temperature of a spinel ferrite film material and belongs to the field of information material technology. Before a spinel-structured ferrite film is prepared on the substrate of the invention, a buffer layer film of Fe3O4 is prepared on the substrate. When a processing of annealing and crystallization is conducted to the spinel-structured ferrite film, the heat released from an activated phase transition from Fe3O4 to Fe2O3 happening to the buffer layer of Fe3O4 is utilized to accelerate the crystallization of the spinel-structured ferrite film, thereby reducing the temperature for the processing of annealing and crystallization for the spinel-structured ferrite film and leaving the spinel-structured ferrite film compatible with the modern micro-electronics technique. Simultaneously, the buffer layer of Fe3O4 belongs to the spinel-structured ferrite film and matches with the crystal lattice of the spinel-structured ferrite film, thereby leaving the introduction of the buffer layer of Fe3O4 having no effect on the excellent electromagnetic property of the spinel-structured ferrite film. The invention is applicable to the preparation of integrated magnetic devices.

Description

A kind of preparation method who reduces annealing temperature of spinel ferrite thin film material
Technical field
The invention belongs to the information material technical field, relate to the preparation method of spinel structure ferrite film.
Background technology
Along with the fast development of modern communications technology, the filming of electronic devices and components, integrated, high frequencyization will make ferrite film have ample scope for one's abilities.High-density perpendicular magnetic recording medium, thin-film head, film transformer and thin film inductor, monolithic microwave integrated device, multilayer film device and biotechnology, medical diagnosis technology, magnetic and medicated development will further be accelerated the paces of ferrite film research.Simultaneously, deposited iron ferrite thin film technology will be one of crucial research contents.See that with regard to application point of view key is to develop on the substrate of different sorts, shape, low temperature depositing has the ferrite film technology of good adhesion and electromagnetic performance.
The preparation method of ferrite film is divided into physical method and chemical process.Physical method mainly comprises sputtering method, pulsed laser deposition, molecular beam epitaxy.With the sedimentary ferrite film of physical method have that substrate sticking power is good, surfacing, characteristics that electromagnetic performance is good, but the shortcoming of the maximum that physical method exists is by high temperature annealing film to be carried out anneal in order to prepare after the ferrite film with good electrical magnetic property need increase temperature or deposit when depositing, and temperature is up to more than 700 ℃.Chemical method mainly comprises wet chemistry method and liquid phase epitaxial method, wherein the ferrite film of liquid phase epitaxial method preparation since during preparation be adopt can with the special substrate of ferrite thin film material lattice constant match, the film of its preparation is monocrystal thin films, thereby be a kind of preparation method of the present energy the most excellent ferrite film of processability, but this method is strict to the substrate restriction, and its preparation is by carrying out after each component melts of ferrite, its temperature very high (～1500 ℃), this is just so that cost is very high on the one hand, application obtains restriction on the other hand, the most fatal is can not with existing microelectronic technique compatibility.Wet chemical method in the chemical preparation process, can obtain ferrite film at low temperature (less than 100 ℃), it is the up-and-coming method of the small-sized integrated device of preparation, but the sticking power between film and substrate is not ideal enough, the rete peeling phenomenon appears easily, so that can't realize using, the surfaceness of the ferrite film of this method preparation is also very big on the other hand, can reduce the electromagnetic performance of ferrite film greatly.
So, it is biggest obstacle on it is used that the high performance ferrite film needs high temperature preparation, high treatment temp not only with existing technology, incompatible as microelectronic technique, and because high treatment temp, can cause the mutual diffusion between substrate and the ferrite film, reduce the electromagnetic performance of ferrite film.It is most important how to realize that low temperature preparation has a good electrical magnetic properties ferrite film.
Summary of the invention
The objective of the invention is to: propose a kind of preparation method who reduces annealing temperature of spinel ferrite thin film material, this method can be reduced to the annealing temperature of spinel structure ferrite film below 500 ℃, can greatly promote the application of ferrite film, the particularly application in the microwave monolithic integrated circuit device.
Principle of the present invention is: Fe 3O 4Be a kind of of ferriferous oxide, its structure is spinel structure, is in metastable state, has lower phase transition temperature, and annealing meeting oxidation generation Fe in the oxygen atmosphere is being arranged more than 400 ℃ 2O 3, its phase transformation reaction formula is: 4Fe 3O 4+ O 2=6Fe 2O 3+ 448 (kJ).If with Fe 3O 4Be cushion, sputter prepares the spinel structure ferrite film on cushion, under 400-500 ℃ of conditions the spinel structure ferrite film is carried out Annealing Crystallization when processing, and cushion can take place from Fe 3O 4To Fe 2O 3Active phase change memory, the heat that phase transformation discharges has been promoted the crystallization of this layer spinel structure ferrite film by upper strata spinel structure ferrite film absorption, thereby reduces the Annealing Crystallization treatment temperature of spinel structure ferrite film.Therefore, spinel structure ferrite thin film technology method provided by the invention can reduce the Annealing Crystallization treatment temperature of spinel structure ferrite film to a great extent, makes it mutually compatible with modern microelectronic technique; Simultaneously, Fe 3O 4Cushion belongs to the spinel strucutre oxides film, with spinel structure ferrite film Lattice Matching, thus so that Fe 3O 4The introducing of cushion does not affect the good electromagnetic property of spinel structure ferrite film.
The present invention realizes as follows:
Step 1. prepares Fe at substrate 3O 4Buffer layer thin film;
Step 2. is at Fe 3O 4Sputter spinel structure ferrite film on the buffer layer thin film;
Step 3. pair spinel structure ferrite film carries out Annealing Crystallization to be processed.
Wherein the substrate in the step 1. can be single crystalline Si, GaAs, InP or the Al of various orientations 2O 3Substrate; Preparation Fe 3O 4The method of buffer layer thin film can adopt magnetron sputtering method, pulsed laser deposition or molecular beam epitaxy; Fe 3O 4The thickness of buffer layer thin film is 20-100nm.
Wherein the condition that sputter prepares the spinel structure ferrite film in the step 2. is: target is the spinel structure ferrite oxide compound of purity more than 98%, and back of the body end vacuum is less than 1 * 10 -3Pa, sputter working gas are argon gas, and air pressure is 1 * 10 -2Pa-5Pa, substrate temperature is 100-350 ℃, sputtering power density is 0.01-10W/cm 2
Wherein the annealing crystallization treatment condition of step 3. are: anneal environment is an air ambient, and annealing temperature is 400-500 ℃, and annealing time is 0.5-3 hours.
The invention has the beneficial effects as follows:
The Annealing Crystallization treatment temperature of the spinel structure ferrite film that spinel structure ferrite thin film technology method provided by the invention can prepare common sputtering technology makes it mutually compatible with modern microelectronic technique from being reduced to below 500 ℃ more than 700 ℃; Simultaneously, Fe 3O 4Cushion belongs to the spinel strucutre oxides film, with spinel structure ferrite film Lattice Matching, thus so that Fe 3O 4The introducing of cushion does not affect the good electromagnetic property of spinel structure ferrite film; The present invention can be used for preparing integrated magnetic device.
Description of drawings
Fig. 1 is Fe 3O 4Buffer layer thin film is through the XRD figure of 350 ℃ of vacuum annealings after one hour.
Fig. 2 is Si/Fe 3O 4/ CoFe 2O 4Film is 400 ℃, 450 ℃ and 500 ℃ of lower annealing XRD figure after 3 hours in air respectively.Wherein, curve 1 is Si/Fe 3O 4/ CoFe 2O 4Film is 400 ℃ of lower annealing XRD results after 3 hours in air; Curve 2 is Si/Fe 3O 4/ CoFe 2O 4Film is 450 ℃ of lower annealing XRD results after 3 hours in air; Curve is 3Si/Fe 3O 4/ CoFe 2O 4Film is 500 ℃ of lower annealing XRD results after 3 hours in air.
Fig. 3 is the Si/Fe of 500 ℃ of lower annealing 3O 4/ CoFe 2O 4The magnetic property curve (VSM curve) of film.
Fig. 4 is the Si/CoFe of 700 ℃ of lower annealing 2O 4The magnetic property curve of film (VSM curve).
Embodiment
At first, prepare oxide ferroelectric thin film with the dc magnetron reactive sputtering method on the Si substrate, processing condition: substrate is Si (a 100) monocrystal chip, back of the body end vacuum 2 * 10 -6Pa; Work atmosphere is the argon gas oxygen, air pressure 1.25 * 10 -2Pa, wherein oxygen accounts for 10%; Sputtering power 200W, sputtering time 45s.Sputtering oxide ferroelectric thin film is 50nm through AFM test thickness.
Secondly, annealing forms Fe in a vacuum 3O 4Buffer layer thin film, processing condition: vacuum tightness 5 * 10 -4Pa, 350 ℃ of annealing temperatures, 1 hour time.Sample after the annealing detects through X-ray diffractometer (XRD) and is the Fe of (110) preferred orientation 3O 4Phase structure (as shown in Figure 1).
Then, at Si/Fe 3O 4Rf magnetron sputtering CoFe on the film 2O 4The spinel structure ferrite film, sputtering condition: 350 ℃ of substrate temperatures, back of the body end vacuum 5 * 10 -4Pa, sputtering atmosphere argon gas, air pressure are 1.0Pa, (corresponding power density is 1.1W/cm to sputtering power 120W 2), sputtering time half an hour.It is 100nm that film after the sputter is tested its thickness through AFM.
At last, Si/Fe 3O 4/ CoFe 2O 4Film is 500 ℃ of lower annealing 3 hours in air, formed the single-phase spinel ferrite body thin film (as shown in Figure 2) of (110) preferred orientation through the XRD test.
For the ease of relatively, under same condition, prepared and do not contained Fe 3O 4CoFe 2O 4Spinel structure ferrite film, i.e. Si/CoFe 2O 4Film is found after tested, at the Si/Fe of 500 ℃ of lower annealing 3O 4/ CoFe 2O 4Film and the Si/CoFe of 700 ℃ of lower annealing 2O 4Film has identical electromagnetic performance (such as Fig. 3 VSM curve).This shows, add Fe 3O 4Behind the cushion so that CoFe 2O 4Spinel structure ferrite Thin-film anneal crystallization temperature has descended 200 ℃, and electromagnetic performance is substantially constant.

Claims (6)

1, a kind of preparation method who reduces annealing temperature of spinel ferrite thin film material, realize as follows:
Step 1. prepares Fe at substrate 3O 4Buffer layer thin film;
Step 2. is at Fe 3O 4Sputter spinel structure ferrite film on the buffer layer thin film;
Step 3. pair spinel structure ferrite film carries out Annealing Crystallization to be processed;
Wherein, the spinel structure ferrite film of sputter preparation is CoFe in the described step 2 2O 4The spinel ferrite body thin film; The Annealing Crystallization treatment conditions of described step 3 are: anneal environment is air ambient, and annealing temperature is 400-500 ℃, and annealing time is 0.5-3 hours.
2, the preparation method of reduction annealing temperature of spinel ferrite thin film material according to claim 1 is characterized in that, the substrate in the described step 1 is single crystalline Si, GaAs, InP or the Al of various orientations 2O 3Substrate; Preparation Fe 3O 4The method of buffer layer thin film is magnetron sputtering method, pulsed laser deposition or molecular beam epitaxy; The Fe of preparation 3O 4Buffer layer thin film thickness is 20-100nm.
3, the preparation method of reduction annealing temperature of spinel ferrite thin film material according to claim 1 and 2, it is characterized in that, sputter prepares the condition of spinel structure ferrite film and is in the described step 2: target is the spinel structure ferrite oxide compound of purity more than 98%, and back of the body end vacuum is less than 1 * 10 -3Pa, sputter working gas are argon gas, and air pressure is 1 * 10 -2Pa-5Pa, substrate temperature is 100-350 ℃, sputtering power density is 0.01-10W/cm 2
4, the preparation method of reduction annealing temperature of spinel ferrite thin film material according to claim 2 is characterized in that, the substrate in the described step 1 is single crystalline Si (100) substrate; Preparation Fe 3O 4The method of buffer layer thin film is the DC magnetron reactive sputtering technique in the magnetron sputtering method; Concrete technology is:
At first, to prepare oxide ferroelectric thin film, processing condition on the dc magnetron reactive sputtering method substrate: back of the body end vacuum 2 * 10 -6Pa; Work atmosphere is the argon gas oxygen, air pressure 1.25 * 10 -2Pa, wherein oxygen accounts for 10%; Sputtering power 200W, sputtering time 45s; The oxide ferroelectric thin film thickness of sputter is 50nm;
Secondly, annealing forms Fe in a vacuum 3O 4Buffer layer thin film, processing condition: vacuum tightness 5 * 10 -4Pa, 350 ℃ of annealing temperatures, 1 hour time.
5, the preparation method of reduction annealing temperature of spinel ferrite thin film material according to claim 1 is characterized in that, described step 2 is at Fe 3O 4Sputter CoFe on the buffer layer thin film 2O 4The concrete technology condition of spinel structure ferrite film: 350 ℃ of substrate temperatures, back end vacuum 5 * 10 -4Pa, sputtering atmosphere argon gas, air pressure are 1.0Pa, sputtering power 120W, corresponding power density is 1.1W/cm 2, sputtering time half an hour; The CoFe of sputter 2O 4Film thickness is 100nm; The actual conditions that described step 3 pair spinel structure ferrite film carries out the Annealing Crystallization processing is: 500 ℃ of temperature, 3 hours time.
6, the preparation method of reduction annealing temperature of spinel ferrite thin film material according to claim 4 is characterized in that, described step 2 is at Fe 3O 4The spinel structure ferrite film of sputter on the buffer layer thin film is CoFe 2O 4The spinel structure ferrite film, concrete technology condition: 350 ℃ of substrate temperatures, back end vacuum 5 * 10 -4Pa, sputtering atmosphere argon gas, air pressure are 1.0Pa, sputtering power 120W, corresponding power density is 1.1W/cm 2, sputtering time half an hour; The CoFe of sputter 2O 4Film thickness is 100nm; The actual conditions that described step 3 pair spinel structure ferrite film carries out the Annealing Crystallization processing is: 500 ℃ of temperature, 3 hours time.
CNB2007100503481A 2007-10-30 2007-10-30 Preparation method lowering annealing temperature of spinel ferrite thin film material Expired - Fee Related CN100519824C (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CNB2007100503481A CN100519824C (en) 2007-10-30 2007-10-30 Preparation method lowering annealing temperature of spinel ferrite thin film material

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CNB2007100503481A CN100519824C (en) 2007-10-30 2007-10-30 Preparation method lowering annealing temperature of spinel ferrite thin film material

Publications (2)

Publication Number Publication Date
CN101230446A CN101230446A (en) 2008-07-30
CN100519824C true CN100519824C (en) 2009-07-29

Family

ID=39897252

Family Applications (1)

Application Number Title Priority Date Filing Date
CNB2007100503481A Expired - Fee Related CN100519824C (en) 2007-10-30 2007-10-30 Preparation method lowering annealing temperature of spinel ferrite thin film material

Country Status (1)

Country Link
CN (1) CN100519824C (en)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102181828B (en) * 2011-04-14 2013-06-12 电子科技大学 Method for preparing ZnFe2O4 ferrite film
CN104030672B (en) * 2014-06-10 2015-11-18 电子科技大学 A kind of preparation method of spinel ferrite body thin film
WO2020010559A1 (en) * 2018-07-12 2020-01-16 深圳先进技术研究院 Thin film with bismuth ferrite solid solution doped at b-site, preparation method therefor and use thereof
CN113235159B (en) * 2021-04-07 2022-07-01 兰州大学 Method for preparing single crystal nickel ferrite film

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5460704A (en) * 1994-09-28 1995-10-24 Motorola, Inc. Method of depositing ferrite film
JP3132915B2 (en) * 1991-09-11 2001-02-05 バイエル・アクチエンゲゼルシヤフト Method for separating polycarbonate with carbon dioxide

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3132915B2 (en) * 1991-09-11 2001-02-05 バイエル・アクチエンゲゼルシヤフト Method for separating polycarbonate with carbon dioxide
US5460704A (en) * 1994-09-28 1995-10-24 Motorola, Inc. Method of depositing ferrite film

Also Published As

Publication number Publication date
CN101230446A (en) 2008-07-30

Similar Documents

Publication Publication Date Title
US20070048440A1 (en) Ferrite thin film for high-frequency devices and production method thereof
CN100519824C (en) Preparation method lowering annealing temperature of spinel ferrite thin film material
CN110021702A (en) A kind of method of quick raising perpendicular magnetic anisotropic
CN102227013A (en) Preparation method of self-supporting multiferroics composite film
CN105331942B (en) Yttrium-iron garnet thin film material and preparation method thereof
KR20170108468A (en) Non rare earth permanent magnet and method for manufacturing the same
KR102125168B1 (en) Hybrid magnetic fiber and fabricating method of the same
Li et al. Structural, electrical and magnetic properties of Gd-doped and (Al, Gd) codoped ZnO films
CN112968058B (en) Ion-regulated spin wave transistor and preparation method thereof
CN113745092A (en) Preparation method of flexible self-supporting perovskite oxide single crystal thin film with different crystal orientations
CN112216507B (en) Preparation method and application of unsupported ferrite magnetic film
CN113192720B (en) Nanoparticle composite magnetic core film and preparation method thereof
CN109234678B (en) Copper-doped barium titanate/nickel zinc ferrite multiphase film material and preparation method thereof
Zhou et al. Fabrication and magnetic properties of Ce1Y2Fe5O12 thin films on GGG and SiO2/Si substrates
RU2655507C1 (en) METHOD FOR OBTAINING FILMS WITH Mn5Ge3OX FERROMAGNETIC CLUSTERS ON THE SUBSTRATE IN THE GeO2 MATRIX
CN101698932B (en) Method for preparing P type cobalt-doped zinc oxide film
CN1412791A (en) Nano composite rare earth permanent magnet film material and its preparation method
JP5660566B2 (en) Magnetic particles and method for producing the same
CN106024972B (en) Semiconductor structure, the method and its application for preparing semiconductor structure
AU2021101181A4 (en) A chemical synthesis method of all-oxide soft-hard magnetic composite film (NZFO/SLCFO)3/Al2O3
Nakagawa et al. Mn–Zn spinel ferrite thin films prepared by high rate reactive facing targets sputtering
CN110042352A (en) A kind of iron-based film superconductor cavity and preparation method thereof
Van Der Zaag et al. The permeability of plated ferrite films
CN113087532B (en) Preparation method of high-performance NiZn ferrite film
CN102061451A (en) Preparation method of L10-FePt granular film

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
C17 Cessation of patent right
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20090729

Termination date: 20111030