CN104818518A - Preparation method of in-plane anisotropy Bi-substituted garnet magneto-optic single crystal thin film - Google Patents
Preparation method of in-plane anisotropy Bi-substituted garnet magneto-optic single crystal thin film Download PDFInfo
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Abstract
The invention aims to provide a preparation method of an in-plane anisotropy Bi-substituted garnet magneto-optic single crystal thin film. The method is used for application of a TE-TM (Transverse Electric-Transverse Magnetic) light mode conversion modulator. A liquid-phase epitaxial process is adopted to realize growth of Bi ion and Lu ion codoped single crystal garnet (BiLuIG) on a gadolinium gallium garnet substrate (orientation of being <111>), a melt reaches the growth temperature of the thin film through a mixing, temperature rising-thermal insulation-triple cooling method, and the growth process of the thin film is controlled to finally prepare the in-plane anisotropy Bi-substituted garnet magneto-optic single crystal thin film. For the growth of the thin film, the three-step cooling mode can achieve good temperature stability and melt state stability. The in-plane anisotropy Bi-substituted garnet magneto-optic single crystal thin film is prepared, the preparation process is simple, and the stability is high.
Description
Technical field
The invention belongs to field of material technology, relate to the preparation method for garnet magneto optical single crystal thin-film material of the Bi with intra-face anisotropy.
Background technology
In recent years, along with the development of technology, the manufacturing process of material is updated, and compared with existing magnetron sputtering technique, PLD technique and sol-gel method, traditional liquid phase epitaxial method (LPE) has irreplaceable effect in prepared by monocrystal thin films.With regard to magneto-optic memory technique, Bi is for garnet magneto optical single crystal thin-film material at integrated magneto-optical device, and the application as aspects such as magneto optic isolator, magneto-optic shutter and magneto-optic modulators is increasing.The film utilizing magnetron sputtering technique to produce has obvious Faraday effect, can be applied to each magnetic-optic devices, but with regard to magneto-optic modulator, can not realize higher efficiency of conversion and larger bandwidth.Compared to magnetron sputtering and PLD sputtering technology, liquid phase epitaxial method can obtain the magneto-optic thin film with substrate matched well, it can not only realize single crystal growing, and desirable thickness can be reached by controlling growth conditions, obtain and there is transparent Bi and the Lu codoped monocrystal thin films of large Faraday angle, low photoabsorption coefficient and near infrared, and then the ultra broadband of magneto-optic modulation and high efficiency of conversion can be realized.Because Bi3+ ion itself has very strong uniaxial anisotropy, therefore Bi is with the easy magnetizing axis of MAGNETIC GARNET FILMS GROWN material to be generally perpendicular in face, but for TE-TM optical mode conversion modulator, need a kind of magneto-optic thin film of intra-face anisotropy, could wide-band modulation be realized.Therefore, based on the application of TE-TM optical mode conversion modulator, we design and the Bi having prepared a kind of intra-face anisotropy for garnet magneto optical single crystal film.
Summary of the invention
The object of the present invention is to provide a kind of Bi of intra-face anisotropy for the preparation method of garnet magneto optical single crystal film, achieve Bi ion and the ion co-doped growth of monocrystalline garnet (BiLuIG) on gadolinium gallium garnet (GGG) substrate base (being oriented to < 111 >) of Lu by liquid phase epitaxial method, achieve the intra-face anisotropy of film.
The technical solution used in the present invention is: a kind of Bi of intra-face anisotropy, for the preparation method of garnet magneto optical single crystal film, comprises the following steps:
Step 1. is filled a prescription, prepare burden: with Lu2O3, Bi2O3, Fe2O3 for raw material, Bi2O3 is flux, and PbO, CaO are additive; According to formula: Bi
xlu
3-xiG, 0<x<3, adopt R factor method of completing the square to carry out batching and obtain melt, the R factor related to has R0, R1, R4, R5, and the relation of four factors is as follows:
Step 2. substrate cleans: adopt organic solution, acid solution, alkaline solution and deionized water to carry out substep cleaning to gadolinium gallium garnet (GGG) substrate successively;
Step 3. melt heating is to film growth temperature: be first warming up to 1000 ~ 1100 DEG C, be incubated 10 ~ 12 hours, then divide and be down to film growth temperature 810 ~ 821 DEG C for three times, the temperature gradient of cooling is followed successively by 80 ~ 140 DEG C, 90 ~ 110 DEG C, 50 ~ 70 DEG C;
Step 4. process of growth controls:
Treat that melt reaches film growth temperature, substrate is placed in melt film growth position, adopt positive and negative rotation substrate method, setting substrate rotating speed is 60 ~ 80rmp, positive and reverse return cycle turnover is 5 ~ 10s, the film growth time is 7 ~ 25min; After growth terminates, substrate is lifted out liquid level, leave standstill 10 ~ 30min at liquid level, obtain the monocrystal thin films of mirror-like;
The post-processed of step 5. film: the mixing solutions film grown being utilized acetic acid and water, cleans 1 ~ 2h under solution hot conditions, removes the molten mass of remained on surface, obtains minute surface film.
Further, the Bi being prepared into intra-face anisotropy is 5 ~ 8um for garnet magneto optical single crystal film thickness.
Further, in described step 5, the ratio of the mixing solutions of acetic acid and water is 1:1.
Further, described film growth temperature is 812 DEG C ~ 817 DEG C.
Preferably, described substrate and fixture have the inclination angle of 3 ~ 5 degree, make film to realize homoepitaxial on the one hand, and after when making growth terminate to propose substrate on the other hand, melt easily flows down.
The present invention adopts liquid phase epitaxial method, the orientation of film growth depends on substrate base GGG, for obtaining high-quality film, require that the film of growth and substrate base can realize maximum lattice match, in formula, the doping of Lu ion and Bi ion calculates according to matching degree.Meanwhile, in the present invention, adopt PbO, CaO as additive, reduce melt solvent temperature on the one hand, realize lesser temps growth; The viscosity of adjustment melt, makes the infiltration angle between melt and substrate moderate, after growth terminates, melt is easily flowed down from substrate on the other hand, improves quality of forming film.In addition, the three step cooling modes that the present invention adopts, for film growth, can obtain good temperature stability and melt state stability.To sum up, the present invention adopts liquid phase epitaxial method, achieve Bi ion and the ion co-doped monocrystalline garnet (BiLuIG) of Lu in the upper growth of gadolinium gallium garnet (GGG) substrate base (being oriented to < 111 >), be prepared into there is intra-face anisotropy Bi for garnet magneto optical single crystal film, preparation technology is simple, and stability is high.
Accompanying drawing explanation
Fig. 1 is the position view of location parameter in process of growth in the specific embodiment of the invention.
Fig. 2 is prepared into BiLuIG film sample in the specific embodiment of the invention, wherein, (a) film thickness is 7.5um, (b) film thickness is 8.1um, (c) film thickness is 9um.
Fig. 3 is the domain structure being prepared into different thickness monocrystal thin films in the specific embodiment of the invention, and wherein, (a) represents the domain structure of 7.5um thickness thin film, (b) represents the domain structure of 9um thickness thin film.
Fig. 4 is the parallel face in rheotaxy BiLuIG magnetic field of the present invention and the M-H graphic representation of vertical face.
Embodiment
Below in conjunction with specific embodiments and the drawings, the present invention is further detailed explanation.
The Bi of intra-face anisotropy, for a preparation method for garnet magneto optical single crystal film, comprises the following steps:
Step 1. is filled a prescription, prepare burden:
Formula is Bi
xlu
3-xiG, according to optimum matching relation, getting x is 0.9; What this embodiment adopted is unleaded extension, with Lu2O3, Bi2O3, Fe2O3 for raw material, i.e. and molten matter, Bi2O3 is flux, and CaO is additive, R0=1, R1=0.1294, R2=0.1751, R3=0.01; The ratio of each composition is determined according to proportioning, and the number of each raw material is determined according to weight proportion and total quality, and the proportion of Bi2O3, Lu2O3, Fe2O3, CaO is followed successively by 92.195%, 1.898%, 5.886%, 0.021%, and total amount is 6000g; Volume because of powder be greater than the volume of melt and crucible size certain, material will divide and add crucible several times, adopt repeatedly filling, thawing, cooling, again filling mode carry out, in order to make melt-mixing even, stir for a long time, until do not have the melt of phase-splitting to occur;
Step 2. substrate cleans:
Adopt gadolinium gallium garnet (GGG) substrate, with trieline, acid solution, alkaline solution and deionized water successively to its cleaning; The object of trieline is the organism removing substrate surface, and acid solution object is that the surface removing substrate is beneficial to film growth, and the object of alkaline solution is to remove the acid solution remaining in substrate surface; Each step has been cleaned and has all been used washed with de-ionized water, avoids previous step to pollute the solution that next step cleans, does not reach cleaning performance;
Step 3. melt heating, heating, cooling to film needs growth temperature point:
In order to make melt-mixing even before growth, stove remains on 1080 DEG C, and the temperature grown required for LuBiIG film is lower than this temperature, and historical facts or anecdotes tests middle employing three step-down warm therapy, reach required growth temperature, this growth temperature is lower than its temperature of saturation (T
s); According to different growth temperatures point, select different falling temperature gradient, and final step cooling should not be too large; Adopt three growth temperatures in the present embodiment respectively, be followed successively by 814.7 DEG C, 819.7 DEG C, 820.7 DEG C, the gradient of cooling is 1080 DEG C-950 DEG C-880 DEG C-814.7 DEG C, 1080 DEG C-950 DEG C-875 DEG C-819.7 DEG C, 1080 DEG C-950 DEG C-876 DEG C-820.7 DEG C;
Step 4. process of growth controls:
First substrate position is determined, be illustrated in figure 1 location parameter schematic diagram, agitator 3 is first utilized to find melt 1 and its point of contact 4 (TP), then according to the design of TP, melt height and fixture, determine that substrate 2 rests on distance 5 (Above Melt Contact) on liquid level, starts growth position 6 (Melt Contact), growth position 7 (GP); As shown in Figure 1,8 is the central position of GGG substrate, 9 is fixture, 10 for fixture 9 decline zero positions (for 0mm), with the zero position declined for benchmark, the point of contact 4 of the lower-most point of fixture 9 and the point of contact of melt and agitator 3 is at same position, and also namely fixture 9 and agitator 3 have identical height; Above Melt Contact=TP-(5 ~ 15mm), Melt Contact=TP+ (26 ~ 30mm), GP=TP+ (48 ~ 52mm); Set in the present embodiment: Melt Contact=TP+28mm, GP=TP+50mm, Above Melt Contact=TP-15mm;
When temperature reaches the growth temperature of setting, the substrate being bind to platinum fixture is moved to Above MeltContact position on liquid level lentamente, avoid too fast decline on the impact of substrate and vitellarium temperature;
Determine to grow rotating speed, rotating speed is directly proportional to the square root of growth velocity, setting rate of rotation is 80rmp, and positive and reverse return cycle turnover is 5s;
Set growth time successively at three growth temperatures 814.7 DEG C, 819.7 DEG C, 820.7 DEG C and be followed successively by 11.7min, 16.2min, 19.2min; Final acquisition thickness is the magneto optical single crystal foamed film of 7.5um, 8.1um, 9um;
After growth terminates, substrate leaves standstill 20min on liquid level, is slowly carried by substrate to furnace chamber mouth afterwards, after leaving standstill several minutes, is rotated by substrate, leaves furnace chamber mouth, avoid the temperature difference to cause substrate to break;
Step 5. film post-processed:
The film grown utilizes the mixing solutions of acetic acid and water (ratio is 1:1) to process in a heated condition, removes the melt residue of film surface, the minute surface obtained; Guarantee that the temperature difference of solution and substrate should not be too large, to prevent substrate from breaking, solution is heated to the state of boiling to clean, and state of at this moment cleaning is the most desirable, is taken off by substrate, weighs, calculates after cleaning up.The film sample grown under Figure 2 shows that above-mentioned condition.
As shown in Figure 3, utilize scanning electronic microscope can see the domain structure of film, LuBiIG film is the film of plane magnetization, (a) stripedomain structure for observing during 7.5um; B mixing farmland that () is the stripedomain that observes during 9um and column farmland.Compared to column farmland, stripedomain can better realize intra-face anisotropy.
As shown in Figure 4, utilize the magnetic hysteresis loop of vibrations sample magnetometer (VSM) measure sample, as can be seen from M ~ H graph of a relation, the film grown has obvious intra-face anisotropy.
Claims (5)
1. the Bi of intra-face anisotropy is for a preparation method for garnet magneto optical single crystal film, comprises the following steps:
Step 1. is filled a prescription, prepare burden: with Lu2O3, Bi2O3, Fe2O3 for raw material, Bi2O3 is flux, and PbO, CaO are additive; According to formula: Bi
xlu
3-xiG, 0<x<3, adopt R factor method of completing the square to carry out batching and obtain melt, the R factor related to has R0, R1, R4, R5, and the relation of four factors is as follows:
Step 2. substrate cleans: adopt organic solution, acid solution, alkaline solution and deionized water to carry out substep cleaning to gadolinium gallium garnet (GGG) substrate successively;
Step 3. melt heating is to film growth temperature: be first warming up to 1000 ~ 1100 DEG C, be incubated 10 ~ 12 hours, then divide and be down to film growth temperature 810 ~ 820 DEG C for three times, the temperature gradient of cooling is followed successively by 80 ~ 140 DEG C, 90 ~ 110 DEG C, 50 ~ 70 DEG C;
Step 4. process of growth controls:
Reach after film growth temperature until melt, with fixture, substrate is placed in melt film growth position, adopt positive and negative rotation substrate method, setting substrate rotating speed is 60 ~ 80rmp, and positive and reverse return cycle turnover is 5 ~ 10s, and the film growth time is 7 ~ 25min; After growth terminates, substrate is lifted out liquid level, leave standstill 10 ~ 30min, obtain the monocrystal thin films of mirror-like;
The post-processed of step 5. film: the mixing solutions film grown being utilized acetic acid and water, cleans 1 ~ 2h under solution hot conditions, removes the molten mass of remained on surface, obtains minute surface film.
2. press the Bi of intra-face anisotropy described in claim 1 for the preparation method of garnet magneto optical single crystal film, it is characterized in that, the Bi being prepared into intra-face anisotropy is 5 ~ 8um for garnet magneto optical single crystal film thickness.
3. press the Bi of intra-face anisotropy described in claim 1 for the preparation method of garnet magneto optical single crystal film, it is characterized in that, in described step 5, the ratio of the mixing solutions of acetic acid and water is 1:1.
4. press the Bi of intra-face anisotropy described in claim 1 for the preparation method of garnet magneto optical single crystal film, it is characterized in that, in described step 3, film growth temperature is 812 DEG C ~ 817 DEG C.
5. press the Bi of intra-face anisotropy described in claim 1 for the preparation method of garnet magneto optical single crystal film, it is characterized in that, in described step 4, substrate and fixture have the inclination angle of 3 ~ 5 degree.
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Cited By (6)
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| CN107146761A (en) * | 2017-05-05 | 2017-09-08 | 电子科技大学 | The yttrium iron garnet of a kind of large magneto-optical effect/bismuth heterofilm and preparation method thereof |
| CN107299394A (en) * | 2017-06-01 | 2017-10-27 | 电子科技大学 | The liquid phase epitaxy preparation method of easy magnetization monocrystalline garnet magneto-optic thin film outside submicron order face |
| CN108736063A (en) * | 2018-06-04 | 2018-11-02 | 北京化工大学常州先进材料研究院 | Tinbase mixes the preparation method of bismuth carbuncle type solid electrolyte material |
| CN111424317A (en) * | 2020-04-13 | 2020-07-17 | 电子科技大学 | Preparation method of single crystal garnet film with high laser-induced damage threshold |
| CN114686983A (en) * | 2021-12-06 | 2022-07-01 | 电子科技大学长三角研究院(湖州) | Preparation method of garnet-phase-doped magneto-optical and nonlinear optical material |
| CN115522262A (en) * | 2022-09-30 | 2022-12-27 | 电子科技大学 | Method for quickly producing imaging single crystal wafer for magneto-optical sensing |
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2015
- 2015-04-17 CN CN201510182491.0A patent/CN104818518A/en active Pending
Non-Patent Citations (4)
| Title |
|---|
| HUAIWU ZHANG ET AL.: "Microwave/Millimeter-Wave Garnet Films", 《IEEE TRANSCTIONS ON MAGNETICS》 * |
| I.I. SYVOROTKA ET AL.: "Growth Peculiarities and Magnetic Properties of (LuBi)3Fe5O12 Films by LPE Method", 《SOLID STATE PHENOMENA》 * |
| KAZUMASA IIDA ET AL.: "Liquid Phase Epitaxial Growth of (Bi, Lu)3(Fe, Ga)5O2 Films with In-Plane Anisotropy for Magneto-Optical Imaging", 《JAPANESE JOURNAL OF APPLIED PHYSICS》 * |
| P. HANSEN ET AL.: "Magnetic and magneto-optical properties of bismuth-substituted lutetium iron garnet films", 《PHYSICAL REVIEW B》 * |
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| CN107146761A (en) * | 2017-05-05 | 2017-09-08 | 电子科技大学 | The yttrium iron garnet of a kind of large magneto-optical effect/bismuth heterofilm and preparation method thereof |
| CN107146761B (en) * | 2017-05-05 | 2020-07-28 | 电子科技大学 | Preparation method of yttrium iron garnet/bismuth heterogeneous film with giant magneto-optical effect |
| CN107299394A (en) * | 2017-06-01 | 2017-10-27 | 电子科技大学 | The liquid phase epitaxy preparation method of easy magnetization monocrystalline garnet magneto-optic thin film outside submicron order face |
| CN108736063A (en) * | 2018-06-04 | 2018-11-02 | 北京化工大学常州先进材料研究院 | Tinbase mixes the preparation method of bismuth carbuncle type solid electrolyte material |
| CN111424317A (en) * | 2020-04-13 | 2020-07-17 | 电子科技大学 | Preparation method of single crystal garnet film with high laser-induced damage threshold |
| 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 |
| CN114686983A (en) * | 2021-12-06 | 2022-07-01 | 电子科技大学长三角研究院(湖州) | Preparation method of garnet-phase-doped magneto-optical and nonlinear optical material |
| CN114686983B (en) * | 2021-12-06 | 2023-08-18 | 电子科技大学长三角研究院(湖州) | Preparation method of garnet-phase doped magneto-optical and nonlinear optical material |
| CN115522262A (en) * | 2022-09-30 | 2022-12-27 | 电子科技大学 | Method for quickly producing imaging single crystal wafer for magneto-optical sensing |
| CN115522262B (en) * | 2022-09-30 | 2024-03-12 | 电子科技大学 | Method for rapidly producing imaging monocrystalline wafer for magneto-optical sensing |
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