CN101319390B - Preparation method of leadless lutetium bismuth carbuncle thin film - Google Patents

Preparation method of leadless lutetium bismuth carbuncle thin film Download PDF

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CN101319390B
CN101319390B CN 200810044640 CN200810044640A CN101319390B CN 101319390 B CN101319390 B CN 101319390B CN 200810044640 CN200810044640 CN 200810044640 CN 200810044640 A CN200810044640 A CN 200810044640A CN 101319390 B CN101319390 B CN 101319390B
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preparation
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bismuth
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CN101319390A (en
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杨青慧
张怀武
刘颖力
文岐业
李元勋
贾利军
苏桦
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University of Electronic Science and Technology of China
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Abstract

The invention provides a method for preparing a lead-free lutetium and bismuth johnstonotite membrane, belonging to the electronic material filed, in particular relating to the johnstonotite membrane material liquid phase extension preparation technique. The method comprises the following steps that: step 1, the preparation of a fused mass, during which, the high-purity oxide raw materials of Lu2O3 and Bi2O3 are weighed, ground, mixed, melted down and placed, and the temperature is reduced to the growth temperature; step 2, a GGG substrate is washed; step 3, the washed substrate and the fused mass liquid level are kept with an angle of between 3 and 15 degrees, the washed substrate is put into the fused mass slowly for the epitaxial growth; step 4, in the process of growth, the substrate rotates at a rate of between 60 and 100 RPM, after the preset growth time reaches, the substrate is lifted off from the fused mass liquid surface slowly; step5, after the growth is over, the substrate rotates at a high speed to shake off the rudimental liquid on the substrate, and then the substrate is lifted off from an epitaxial furnace slowly to avoid the membrane cleavage caused by the heat expansion; and step 6, the membrane is washed by a hot nitric acid to remove the residual Bi2O3 fusing agent.

Description

Preparation method of leadless lutetium bismuth carbuncle thin film
Technical field
The invention belongs to field of electronic materials, particularly the rheotaxy technology of preparing of garnet thin film material.
Background technology
Garnet series thin film through the liquid phase epitaxy method preparation has been used the long duration in magnetic-optic devices and microwave device, such as shifter, optoisolator, magneto-optic shutter, microwave circulator, shield retaining and magnetic static wave wave filter, retarding line etc.At present, the major applications of YIG series thin film is all merely based on its magneto-optical property or microwave property, yet along with the fast development of magneto-optic and microwave integrated circuit, is badly in need of a kind of garnet film that has good magneto-optic effect and microwave property simultaneously concurrently.On the other hand, the used fusing assistant of rheotaxy is generally PbO-B 2O 3(Bi 2O 3), BaO-BaF 2-B 2O 3And MoO 3-Li 2O is because PbO-B 2O 3(Bi 2O 3) high growth rates and the low growth temperature of fusing assistant, become the most frequently used fusing assistant.Yet the PbO fusing assistant has strong volatility, and toxicity and corrodibility also can be polluted film simultaneously, and the magneto-optical property and the microwave property of film brought a series of negative impact.
Summary of the invention
Technical problem to be solved by this invention is a kind of LuBiIG garnet method for manufacturing thin film that has good magneto-optical property and microwave property simultaneously to be provided, the rheotaxy technology of preparing of employing lead-free process.
The technical scheme that the present invention solve the technical problem employing is that preparation method of leadless lutetium bismuth carbuncle thin film may further comprise the steps:
The preparation of step 1 melt: by predefined mol ratio, accurate weighing high pure oxide raw material Lu 2O 3And Bi 2O 3, to grind, mixed back reduces temperature to growth temperature then in 1000 ℃-1050 ℃ fusings and placement;
Step 2 is cleaned the GGG substrate;
Step 3 keeps 3-15 ° with cleaned substrate and melt liquid level, slowly puts into melt, prepares epitaxy;
Step 4 is in process of growth, and substrate rotates with 60-100 rev/min speed, reach preset growth time after, substrate is slowly lifted from melt liquid level;
Behind the step 5 growth ending,,, from epitaxial furnace, slowly mention substrate then and avoid owing to thermal expansion causes the film cracking to get rid of on-chip residual drop with the substrate high speed rotating;
Step 6 cleans film to remove remaining Bi in hot nitric acid 2O 3Fusing assistant.
Further, step 2 comprises:
(1) with deionized water ultrasonic cleaning 15min; (2) repeat (1); (3) with acetone ultrasonic cleaning 15min; (4) repeat (3); (5) with the clear ultrasonic cleaning 15min of wine.(6) repeat (5); (7) boil with the vitriol oil+nitric acid; (8) with flushing of lot of pure water and oven dry.
In the step 4, regularly change sense of rotation, changed once in promptly every separated several minutes.
The invention has the beneficial effects as follows that the ferromagnetic resonance line width of the thin-film material through preparation of the present invention is less than 3Oe, faraday's rotation angle can reach 1.64deg/ μ m when 633nm, and when wavelength during greater than 800nm, photoabsorption coefficient is less than 170cm -1, saturation magnetization is in the 1550-1570Gs scope, and fine and close, the surfacing of membrane structure simultaneously is to be applied to the elite clone in magnetic-optic devices and the microwave device simultaneously.Compare with other garnet thin film material, the film of the present invention's preparation has good magneto-optic effect and narrow ferromagnetic resonance line width simultaneously, both may be used on can be applicable in the microwave device again in the magnetic-optic devices; The lutetium bismuth carbuncle film adopts the liquid phase epitaxy method preparation, and the lattice parameter between film and the substrate and the matching degree of thermal expansivity are fine, and the film of preparation is the monocrystalline attitude.
Below in conjunction with embodiment and accompanying drawing the present invention is further described.
Description of drawings
Fig. 1 rheotaxy furnace structure synoptic diagram.
The lattice parameter of Fig. 2 LuBiIG film is with the change curve of Bi content.
The XRD test analysis graphic representation of lattice constant match degree between Fig. 3 LuBiIG film and the GGG substrate.
Ferromagnetic resonance line width test (ball hole method) graphic representation of Fig. 4 LuBiIG film.
Faraday's rotation angle of Fig. 5 LuBiIG film and the graph of relation between the externally-applied magnetic field (λ=633nm).
The photoabsorption coefficient of Fig. 6 LuBiIG film is with the wavelength change graphic representation.
Embodiment
The LuBiIG thin-film material that the present invention proposes is to utilize the liquid phase epitaxy method preparation, and its processing unit is as shown in Figure 1, wherein, and phonomoter 1, GGG substrate 2, well heater 3, crucible 4, melt 5, ceramic lifting rod 6.
Concrete preparation process is:
Step 1, melt preparation: press the mol ratio of definition such as Blank, with high pure oxide raw material Lu 2O 3And Bi 2O 3Accurately weighing is carefully ground in agate mortar, mixed being placed in platinum (Pt) crucible, fusing and placing 24 hours in 1000 ℃-1050 ℃ Platinum crucible, simultaneously in order to make the solution temperature homogeneous, with the platinum rod 1000 ℃ of stirrings 12 hours.Reduce by 803 ℃ of temperature to growth temperatures then.
Step 2, consider lattice and matched coefficients of thermal expansion between substrate and the garnet film, selected for use to reach other gadolinium gallium garnet of extension level (GGG) substrate.At first pre-treatment is carried out on the surface of substrate, cleaning step is:
(1) with deionized water ultrasonic cleaning 15min; (2) repeat (1); (3) with acetone ultrasonic cleaning 15min; (4) repeat (3); (5) with the clear ultrasonic cleaning 15min of wine.(6) repeat (5); (7) boil with the vitriol oil+nitric acid; (8) with flushing of lot of pure water and oven dry.
Step 3, cleaned substrate is fixed on the support with platinum wire.Substrate and melt liquid level keep a small angle (3-15 °), slowly put into melt, prepare epitaxy.
Step 4, in process of growth, substrate rotates with 60-100 rev/min speed, every at a distance from sense of rotation change in 3 minutes once.After reaching preset growth time, substrate is slowly lifted from melt liquid level.
Behind step 5, the growth ending, with the substrate high speed rotating, to get rid of on-chip residual drop.From epitaxial furnace, slowly mentioning substrate then avoids owing to thermal expansion causes the film cracking.
Step 6, film is cleaned in hot nitric acid to remove remaining Bi 2O 3Fusing assistant.
Can find out along with the increase with Bi content of the lattice parameter of LuBiIG film increases by Fig. 2, work as Lu 2.1-xBi xFe 5O 12During x=0.9, this moment, the lattice parameter of film was all 12.383 mutually with the lattice parameter of substrate
Figure S2008100446407D00041
The lattice match degree is good, and can obtain the epitaxial film of excellent property this moment.
XRD curve by Fig. 3 film and substrate can find out that the matching degree between substrate and the film is fine, and the mismatch degree is 0.8%.
Can find out that by Fig. 4 the ferromagnetic resonance line width of film is 2.5Oe, is applied in the microwave device for film, can make the transmission loss of device very low, thereby obtain the gyromagnetic device of excellent property.
Can find out that by Fig. 5 when externally-applied magnetic field intensity during less than 180mT, the faraday angle of film increases along with the increase in magnetic field is linear, magnetic field greater than 180mT after, the faraday angle θ of film fBe steady state value θ f=1.6deg/ μ m, compared to adopting PbO to do the film that fusing assistant generates, improve greatly at its faraday angle.
Can find out that by Fig. 6 the maximum absorption coefficient of film is 600-650cm -1, and along with the increase of wavelength, its uptake factor reduces.Compared to adopting PbO to do the film that fusing assistant generates, its uptake factor reduces greatly.

Claims (3)

1. preparation method of leadless lutetium bismuth carbuncle thin film is characterized in that, may further comprise the steps:
Step 1 melt preparation: press the mol ratio of Blank definition, accurately weighing high pure oxide raw material Lu 2O 3And Bi 2O 3, to grind, mixed back reduces by 803 ℃ of temperature to growth temperatures then in 1000 ℃-1050 ℃ fusings and placement;
Step 2 is cleaned the GGG substrate;
Step 3 keeps 3-15 ° with cleaned substrate and melt liquid level, slowly puts into melt, prepares epitaxy;
Step 4 is in process of growth, and substrate rotates with 60-100 rev/min speed, reach preset growth time after, substrate is slowly lifted from melt liquid level;
Behind the step 5 growth ending,,, from epitaxial furnace, slowly mention substrate then and avoid owing to thermal expansion causes the film cracking to get rid of on-chip residual drop with the substrate high speed rotating;
Step 6 cleans film to remove remaining Bi in hot nitric acid 2O 3Fusing assistant.
2. preparation method of leadless lutetium bismuth carbuncle thin film as claimed in claim 1 is characterized in that, said step 2 comprises:
(1) with deionized water ultrasonic cleaning 15min;
(2) repeat (1);
(3) with acetone ultrasonic cleaning 15min;
(4) repeat (3);
(5) with the clear ultrasonic cleaning 15min of wine.
(6) repeat (5);
(7) boil with the vitriol oil+nitric acid;
(8) with flushing of lot of pure water and oven dry.
3. preparation method of leadless lutetium bismuth carbuncle thin film as claimed in claim 1 is characterized in that, in the rotary course of step 4, whenever changes sense of rotation at a distance from 3 minutes.
CN 200810044640 2008-06-06 2008-06-06 Preparation method of leadless lutetium bismuth carbuncle thin film Expired - Fee Related CN101319390B (en)

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CN104831357B (en) * 2015-04-15 2017-10-17 电子科技大学 A kind of yig single crystal film and preparation method thereof
CN104820298B (en) * 2015-04-17 2018-01-12 电子科技大学 A kind of TM TE magneto-optic modulators based on BiLuIG films
CN104775160A (en) * 2015-04-27 2015-07-15 电子科技大学 Preparation method of monocrystalline garnet thick film
CN104775153A (en) * 2015-05-08 2015-07-15 西南应用磁学研究所 Novel magneto-optic single crystal material growing method
CN111424317B (en) * 2020-04-13 2021-08-06 电子科技大学 Preparation method of single crystal garnet film with high laser-induced damage threshold
CN114657631A (en) * 2022-03-28 2022-06-24 电子科技大学 Preparation method of bismuth-substituted rare earth iron garnet single crystal thick film

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CN1329184A (en) * 2000-06-06 2002-01-02 株式会社东金 Bismuth-substituted garnets thick film material and producing method thereof

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