CN101319389B - Preparation method of gadolinium gallium garnet planar interface crystal - Google Patents
Preparation method of gadolinium gallium garnet planar interface crystal Download PDFInfo
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- CN101319389B CN101319389B CN2008100444276A CN200810044427A CN101319389B CN 101319389 B CN101319389 B CN 101319389B CN 2008100444276 A CN2008100444276 A CN 2008100444276A CN 200810044427 A CN200810044427 A CN 200810044427A CN 101319389 B CN101319389 B CN 101319389B
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Abstract
The invention discloses a method for preparing a gadolinium gallium garnet (GGG) planar interface crystal, belonging to the optical crystal technical field. The method comprises the following steps that: CaO and/or MgO and ZrO2 are doped in a raw material formula of the GGG crystal and a manual controlled interface converting technology method is used so that the planar interface doped large lattice parameter GGG crystal with good stress and internal quality is grown. The calcium-magnesium-zirconium doped large lattice parameter GGG planar interface crystal with a diameter more than 2 inches and a length more than 120 millimeters is grown by the method. The crystal has good internal quality, even stress, and zero dislocation, does not observe any scattering particle under the He-Ne light, has a lattice parameter of between 12.383 and 12.620, and the change in the crystal head and tail lattice parameters is within 10<-2>. The method is particularly suitable for the large lattice parameter (Ca, Mg and Zr) of an epitaxial substrate: GGG crystal growth field.
Description
Technical field
The present invention relates to a kind of optical crystal, particularly relate to a kind of doping GGG crystal technology field that is used for magnetic-optic devices and bubble domain memory device.
Background technology
Mix bismuth and other adulterated class iron garnet (Bi:RIG) epitaxy single-crystal film, be considered to be used at present the best magneto-optic memory technique of optical communication technology because of it has bigger lattice parameter, low saturation magnetic field, good temperature stability than traditional yttrium iron garnet (YIG).But because the increase of its lattice parameter (generally all exists
More than), less as pure gadolinium gallium garnet (GGG) crystal of the epitaxial base bottom material of traditional yig single crystal film because of its lattice parameter
Be not suitable as the requirement of the epitaxial substrate of class iron garnet single crystal film.Of the present invention and the gadolinium gallium garnet of mixing calcium magnesium zirconium (Zr:GGG) crystal as required, is selected different prescriptions for Ca, Mg, its lattice parameter can
Between adjust, therefore can satisfy of the requirement of different doping Bi:RIG monocrystal thin films to epitaxial substrate.As everyone knows, the quality of monocrystal thin films quality depends on the quality of epitaxial substrate to a great extent.The GGG crystal is because the physicochemical characteristic of its melt and crystalline thermal conductivity the subject of knowledge and the object of knowledge are definite, in process of growth, be easy to take place solid-liquid interface by protruding to flat conversion naturally, and the switching process of this solid-liquid interface often is accompanied by intensive liquid stream and variation of temperature, thereby the variation that causes the crystals quality, even cracking.Though can grope processing condition, avoid the generation of this process, make crystal keep the dimpling interface growth, but still there is certain core stress in its centre portions of the crystal of this dimpling interface growth, and because the inhomogeneous lattice parameter that causes of solute distribution inhomogeneous.Thereby influence the optical quality of epitaxial substrate.
Summary of the invention
The objective of the invention is to: a kind of special technological measure that adopts is provided, artificial control crystalline interface conversion, and by the interruption of processing parameter and/or variation continuously, make crystal be in growth under the more stable planar interface state all the time, thereby overcome the defective that the crystal mass variation that causes is changed at natural interface not controlled in the above-mentioned existing Technology, grow the good adulterated macrolattice constant GGG crystal of optical homogeneity, the preparation method of a kind of gadolinium gallium garnet planar interface crystal of fine magneto-optic thin film epitaxial substrate material is provided for the development of laser and optical communication technology.
Technical scheme of the present invention is: a kind of preparation method of gadolinium gallium garnet planar interface crystal comprises following processing step: 1. raw material comprises the GGG crystal, CaO and/or MgO, ZrO
2, the purity of each component is as follows, presses each component of following proportioning (mole) weighing:
Feed molar purity
Gd
2O
3 3(1-x/3) 4.5N
Ga
2O
3 5(1.02-y/5-z/5) 4.5N
CaO 2x analytical pure
MgO 2y analytical pure
ZrO
2The 2z analytical pure
Wherein, the span of x: 0～0.75mol, the span of y: 0～0.75mol, the span of z: 0.01～1.5mol;
2. load weighted each component raw material is mixed in the multilayer latex rubber bag of packing into, after cold isostatic press compression moulding, 1100～1300 ℃ of sintering temperature reactions 10～15 hours;
3. go in the single crystal growing furnace the above-mentioned material that sinters is packaged, charge into argon gas after vacuumizing, wait to expect to charge into oxygen after the heat fused, wherein, the intrinsic standoff ratio of oxygen and argon gas is (1～5): (99～95), open flow atmosphere control device then;
4. the crystalline style rotating speed is set is 8～15rpm, and pull rate is 0.5～3.5mm/h, and crystal is automatically seeding shouldering and change isometrical protruding interface growth in single crystal growing furnace; When the isodiametric growth 15～30mm of the protruding interface of crystal, change manual state over to, implement Artificial Control interface conversion process, comprise that processing step is as follows:
A. stop to lift, promptly the crystal pulling rate is reduced to zero;
B. pre-temperature adjustment, according to the difference of crystal diameter and thermal field, its temperature adjustment amplitude is in-100～+ 50 ℃ of scopes;
C. rotating speed: 15～50rpm resets;
D. temperature adjustment, its temperature adjustment amplitude are generally in-20～+ 20 ℃ of scopes;
E. divide the sinking crystal 3～4 times, the 0.5～2.0mm that at every turn sinks, and the temperature variations of looking each after the sinking carries out temperature adjustment, tends to balance until temperature;
F. change auto state over to, crystal begins plane interface growth, pull rate 0.1～5.0mm/h;
5. growth ending, on shake crystal 8～15mm, slowly be cooled to room temperature, take out crystal.
The temperature of described e step tends to balance the deviation range that is meant the diameter before the conversion of crystal diameter and crystal interface in ± the 0.5mm.
The controlled step of the auto state of described f step is: the fs, the crystalline style speed range is 15～50rpm, crystal plane interface growth length range is 10～30mm, and the crystalline style pull rate is from the zero line increase, and the maximum value that this crystalline style pull rate allows to be increased to is 5.0mm/h; Subordinate phase, the rotating speed of crystalline style rotating speed and fs is identical, crystal plane interface growth length range 30～50mm, the crystalline style pull rate keeps the maximum value of fs pull rate constant; Phase III, the crystalline style rotating speed reduces from the rotating speed of subordinate phase is linear, the minimum value that this rotating speed allows to be reduced to is 15rpm, crystal plane interface growth length range is 40～60mm, pull rate reduces from the pull rate value of subordinate phase is linear, and the minimum value that this pull rate allows to be reduced to is 0.1mm/h.
CaO and MgO can select for use wherein a kind ofly in the raw material of the present invention, also can two kinds adopt simultaneously.
Principle of work of the present invention: in GGG crystalline composition of raw materials, mix ZrO
2CaO and/or MgO, pass through ionic replacement, reach the purpose that increases the crystal lattices constant, it promptly mainly is the principle of utilizing ion to replace, usually increase lattice parameter by the unit of mixing the heavy ion radius, and by means of a kind of manually operated interface conversion process measure, implement a kind of special processing step at the common isodiametric growth of crystal initial stage, realize the controlled conversion of crystal solid-liquid interface, thereby make crystal keep more stable plane interface growth state, grow the good planar interface doping macrolattice constant GGG crystal of stress and internal soundness.
The invention has the beneficial effects as follows: grown diameter greater than 2 inches with present method, length is greater than the macrolattice constant gadolinium gallium garnet planar interface crystal of mixing calcium magnesium zirconium of 120mm, and the crystals quality is good: stress is even; Zero dislocations; Do not observe scattering particles under the He-Ne light, its lattice parameter is 12.383～12.620, and the crystal variation of lattice parameter end to end exists
In.
The present invention is further described below by embodiment.
Embodiment
Embodiment 1
A kind of preparation method of gadolinium gallium garnet planar interface crystal, by following mole proportioning,
Feed molar (mol)
Gd
2O
3 3(1-x/3)
Ga
2O
3 5(1.02-y/5-z/5)
CaO 2x
MgO 2y
ZrO
2 2z
Wherein, choose x=0.32, y=0.33, z=0.65.
Gd by said ratio weighing purity 4.5N
2O
3, Ga
2O
3Reach analytically pure CaO, MgO, ZrO
2, uniform mixing, and in the multilayer latex rubber bag of packing into, after cold isostatic press compression moulding, 1200 ℃ of sintering temperature reactions 10 hours; The single crystal growing furnace of packing into is evacuated to≤10Pa, charges into argon gas, is heated to the raw material fusing, charges into oxygen (intrinsic standoff ratio of oxygen and argon gas is 1: 99), the unlatching gas flow means.It is 8rpm that the crystalline style rotating speed is set, and pull rate is 1.0mm/h, and crystal automatic seeding shouldering in single crystal growing furnace is changeed shoulder and changed isometrical protruding interface growth (crystal diameter Φ 56mm) over to; After the protruding interface of crystal isodiametric growth is long to 25mm, come into effect Artificial Control interface conversion process:
A. stop to lift, promptly the crystal pulling rate is reduced to zero;
B. pre-temperature adjustment, according to the difference of crystal diameter and thermal field, its temperature adjustment amplitude is at-50 ℃;
C. rotating speed: 15rpm resets;
D. temperature adjustment, its temperature adjustment amplitude are generally in+10 ℃ of scopes;
E. divide the sinking crystal 3 times, the 0.5～2.0mm that at every turn sinks, and the temperature variations of looking each after the sinking carries out temperature adjustment, tends to balance until temperature; The deviation range that is the diameter before the conversion of crystal diameter and crystal interface is in ± the 0.5mm;
F. change auto state over to, crystal begins plane interface growth; The controlled step of its auto state is: the fs, and crystalline style rotating speed 15rpm, crystal plane interface growth length 25mm, the crystalline style pull rate is increased to 3.0mm/h from the zero line increase always; Subordinate phase, crystalline style rotating speed are 15rpm, crystal plane interface growth length 50mm, and the crystalline style pull rate keeps the maximum value of fs pull rate constant, is 3.0mm/h; Phase III, crystalline style rotating speed 15rpm, crystal plane interface growth length 45mm, pull rate reduces from the 3.0mm/h of subordinate phase is linear, reduces to 2.0mm/h always.
Growth ending, on shake crystal 15mm, slowly be cooled to room temperature, take out crystal.
The crystal perfection that grows by present method is transparent, uniform internal stress, and the epitaxial substrate of the 2 inches diameter that processes, optical homogeneity is good, does not observe scattering and dislocation.The crystalline lattice parameter is
The variation of whole crystalline lattice parameter less than
Embodiment 2:
A kind of preparation method of gadolinium gallium garnet planar interface crystal, by following mole proportioning,
Feed molar (mol)
Gd
2O
3 3(1-x/3)
Ga
2O
3 5(1.02-y/5-z/5)
CaO 2x
MgO 2y
ZrO
2 2z
Choose x=0.38, y=0.39, z=0.77.
Press the Gd of the purity 4.5N of said ratio weighing
2O
3, Ga
2O
3Reach analytically pure CaO, MgO, ZrO
2, uniform mixing, compression moulding, 1100 ℃ of sintering 15 hours, the single crystal growing furnace of packing into is evacuated to furnace pressure≤10Pa, charges into argon gas, is heated to the raw material fusing, charges into oxygen (intrinsic standoff ratio of oxygen and argon gas is 2: 98), the unlatching gas flow means.It is 12rpm that the crystalline style rotating speed is set, pull rate is 2.5mm/h, crystal automatic seeding shouldering in single crystal growing furnace is changeed shoulder and is changed isometrical protruding interface growth (crystal diameter Φ 53mm) over to, when the protruding interface of crystal isodiametric growth to 25mm length comes into effect Artificial Control interface conversion process:
A. stop to lift, promptly the crystal pulling rate is reduced to zero;
B. pre-temperature adjustment, its temperature adjustment amplitude is at-80 ℃;
C. rotating speed: 30rpm resets;
D. temperature adjustment, its temperature adjustment amplitude is+15 ℃;
E. divide the sinking crystal 3 times, the 0.5～2.0mm that at every turn sinks, and the temperature variations of looking each after the sinking carries out temperature adjustment, tends to balance until temperature; The deviation range that is the diameter before the conversion of crystal diameter and crystal interface is in ± the 0.5mm.
F. change auto state over to, crystal begins plane interface growth; The controlled step of its auto state is: the fs, and crystalline style rotating speed 30rpm, crystal plane interface growth length 30mm, the crystalline style pull rate is increased to 3.0mm/h from the zero line increase always; Subordinate phase, crystalline style rotating speed are 30rpm, crystal plane interface growth length 40mm, pull rate 3.0mm/h; Phase III, the crystalline style rotating speed is reduced to 25rpm from the 30rpm linearity of subordinate phase, crystal plane interface growth length 50mm, and pull rate reduces from the 3.0mm/h of subordinate phase is linear, reduces to 2.0mm/h always.
Growth ending, on shake crystal 12mm, slowly be cooled to room temperature, take out crystal.
The crystal perfection that present embodiment grows is transparent, uniform internal stress, and the epitaxial substrate of the 2 inches diameter that processes, optical homogeneity is good, does not observe scattering and dislocation.The crystalline lattice parameter is
The variation of whole crystalline lattice parameter less than
Embodiment 3:
A kind of preparation method of gadolinium gallium garnet planar interface crystal, by following mole proportioning,
Feed molar (mol)
Gd
2O
3 3(1-x/3)
Ga
2O
3 5(1.02-y/5-z/5)
CaO 2x
MgO 2y
ZrO
2 2z
Choose x=0.45, y=0.46, z=0.91.
Gd by said ratio weighing purity 4.5N
2O
3, Ga
2O
3Reach analytically pure CaO, MgO, ZrO
2, uniform mixing, compression moulding, 1300 ℃ of sintering 12 hours, the single crystal growing furnace of packing into is evacuated to furnace pressure≤10Pa, charges into argon gas, is heated to the raw material fusing, charges into oxygen (intrinsic standoff ratio of oxygen and argon gas is 3: 97), the unlatching gas flow means.It is 10rpm that the crystalline style rotating speed is set, pull rate is 1.5mm/h, crystal automatic seeding shouldering in single crystal growing furnace is changeed shoulder and is changed isometrical protruding interface growth (crystal diameter Φ 53mm) over to, when the protruding interface of crystal isodiametric growth to 25mm length comes into effect Artificial Control interface conversion process:
A. stop to lift, promptly the crystal pulling rate is reduced to zero;
B. pre-temperature adjustment, its temperature adjustment amplitude is at-50 ℃;
C. rotating speed: 25rpm resets;
D. temperature adjustment, its temperature adjustment amplitude is+20 ℃;
E. divide the sinking crystal 3 times, the 0.5～2.0mm that at every turn sinks, and the temperature variations of looking each after the sinking carries out temperature adjustment, tends to balance until temperature; The deviation range that is the diameter before the conversion of crystal diameter and crystal interface is in ± the 0.5mm.
F. change auto state over to, crystal begins plane interface growth; The controlled step of its auto state is: the fs, and crystalline style rotating speed 25rpm, crystal plane interface growth length 20mm, the crystalline style pull rate is increased to 2.5mm/h from the zero line increase always; Subordinate phase, crystalline style rotating speed are 25rpm, crystal plane interface growth length 50mm, pull rate 2.5mm/h; Phase III, the crystalline style rotating speed is reduced to 20rpm from the 25rpm linearity of subordinate phase, crystal plane interface growth length 50mm, and pull rate reduces from the 2.5mm/h of subordinate phase is linear, reduces to 1.5mm/h always.
Growth ending, on shake crystal 10mm, slowly be cooled to room temperature, take out crystal.
The crystal perfection that present embodiment grows is transparent, and uniform internal stress is not observed scattering and dislocation.The crystalline lattice parameter is
The variation of whole crystalline lattice parameter less than
Embodiment 4:
A kind of preparation method of gadolinium gallium garnet planar interface crystal, by following mole proportioning,
Feed molar (mol)
Gd
2O
3 3(1-x/3)
Ga
2O
3 5(1.02-y/5-z/5)
CaO 2x
MgO 2y
ZrO
2 2z
Choose x=0.00, y=0.60, z=0.60.
Gd by said ratio weighing purity 4.5N
2O
3, Ga
2O
3And analytically pure MgO, ZrO
2, uniform mixing, compression moulding, 1200 ℃ of sintering 15 hours, the single crystal growing furnace of packing into is evacuated to furnace pressure≤10Pa, charges into argon gas, is heated to the raw material fusing, charges into oxygen (intrinsic standoff ratio of oxygen and argon gas is 2: 98), the unlatching gas flow means.It is 8rpm that the crystalline style rotating speed is set, pull rate is 3.5mm/h, crystal automatic seeding shouldering in single crystal growing furnace is changeed shoulder and is changed isometrical protruding interface growth (crystal diameter Φ 53mm) over to, when the protruding interface of crystal isodiametric growth to 25mm length comes into effect Artificial Control interface conversion process:
A. stop to lift, promptly the crystal pulling rate is reduced to zero;
B. pre-temperature adjustment, its temperature adjustment amplitude is-50 ℃;
C. rotating speed: 35rpm resets;
D. temperature adjustment, its temperature adjustment amplitude is-10 ℃;
E. divide the sinking crystal 3 times, the 0.5～2.0mm that at every turn sinks, and the temperature variations of looking each after the sinking carries out temperature adjustment, tends to balance until temperature; The deviation range that is the diameter before the conversion of crystal diameter and crystal interface is in ± the 0.5mm.
F. change auto state over to, crystal begins plane interface growth; The controlled step of its auto state is: the fs, and crystalline style rotating speed 35rpm, crystal plane interface growth length 30mm, the crystalline style pull rate is increased to 5.0mm/h from the zero line increase always; Subordinate phase, crystalline style rotating speed are 35rpm, crystal plane interface growth length 40mm, pull rate 5.0mm/h; Phase III, the crystalline style rotating speed is reduced to 25rpm from the 35rpm linearity of subordinate phase, crystal plane interface growth length 50mm, and pull rate reduces near always 2.5mm/h from the 5.0mm/h of subordinate phase is linear.
Growth ending, on shake crystal 10mm, slowly be cooled to room temperature, take out crystal.
The crystal perfection that present embodiment grows is transparent, and uniform internal stress is not observed scattering and dislocation.The crystalline lattice parameter is
The variation of whole crystalline lattice parameter less than
Embodiment 5:
A kind of preparation method of gadolinium gallium garnet planar interface crystal, by following mole proportioning,
Feed molar (mol)
Gd
2O
3 3(1-x/3)
Ga
2O
3 5(1.02-y/5-z/5)
CaO 2x
ZrO
2 2z
Choose x=0.75, y=0.00, z=0.75.
Gd by said ratio weighing purity 4.5N
2O
3, Ga
2O
3And analytically pure CaO, ZrO
2, uniform mixing, compression moulding, 1200 ℃ of sintering 15 hours, the single crystal growing furnace of packing into is evacuated to furnace pressure≤10Pa, charges into argon gas, is heated to the raw material fusing, charges into oxygen (intrinsic standoff ratio of oxygen and argon gas is 3: 97), the unlatching gas flow means.It is 10rpm that the crystalline style rotating speed is set, pull rate 2.5mm/h, crystal automatic seeding shouldering in single crystal growing furnace is changeed shoulder and is changed isometrical protruding interface growth (crystal diameter Φ 52mm) over to, when the protruding interface of crystal isodiametric growth to 25mm length comes into effect Artificial Control interface conversion process:
A. stop to lift, promptly the crystal pulling rate is reduced to zero;
B. pre-temperature adjustment, its temperature adjustment amplitude is at-80 ℃;
C. rotating speed: 40rpm resets;
D. temperature adjustment, its temperature adjustment amplitude is+10 ℃;
E. divide the sinking crystal 4 times, the 0.5～2.0mm that at every turn sinks, and the temperature variations of looking each after the sinking carries out temperature adjustment, tends to balance until temperature; The deviation range that is the diameter before the conversion of crystal diameter and crystal interface is in ± the 0.5mm.
F. change auto state over to, crystal begins plane interface growth; The controlled step of its auto state is: the fs, and crystalline style rotating speed 40rpm, crystal plane interface growth length 25mm, the crystalline style pull rate is increased to 3.5mm/h from the zero line increase always; Subordinate phase, crystalline style rotating speed are 40rpm, crystal plane interface growth length 45mm, pull rate 3.5mm/h; Phase III, the crystalline style rotating speed is reduced to 25rpm from the 40rpm linearity of subordinate phase, crystal plane interface growth length 50mm, and pull rate reduces near always 2.0mm/h from the 3.5mm/h of subordinate phase is linear.
Growth ending, on shake crystal 12mm, slowly be cooled to room temperature, take out crystal.
The crystal perfection that present embodiment grows is transparent, and uniform internal stress is not observed scattering and dislocation.The crystalline lattice parameter is
The variation of whole crystalline lattice parameter less than
Embodiment 6:
A kind of preparation method of gadolinium gallium garnet planar interface crystal, by following mole proportioning,
Feed molar (mol)
Gd
2O
3 3(1-x/3)
Ga
2O
3 5(1.02-y/5-z/5)
MgO 2y
ZrO
2 2z
Choose x=0.00, y=0.75, z=0.75.
Gd by said ratio weighing purity 4.5N
2O
3, Ga
2O
3And analytically pure CaO, ZrO
2, uniform mixing, compression moulding, 1250 ℃ of sintering 13 hours, the single crystal growing furnace of packing into is evacuated to furnace pressure≤10Pa, charges into argon gas, is heated to the raw material fusing, charges into oxygen (intrinsic standoff ratio of oxygen and argon gas is 4: 96), the unlatching gas flow means.It is 10rpm that the crystalline style rotating speed is set, pull rate is 2.5mm/h, crystal automatic seeding shouldering in single crystal growing furnace is also changeed shoulder and is changed isometrical protruding interface growth (crystal diameter Φ 51mm) over to, when the protruding interface of crystal isodiametric growth to 30mm length comes into effect Artificial Control interface conversion process:
A. stop to lift, promptly the crystal pulling rate is reduced to zero;
B. pre-temperature adjustment, its temperature adjustment amplitude is at-80 ℃;
C. rotating speed: 45rpm resets;
D. temperature adjustment, its temperature adjustment amplitude is-20 ℃;
E. divide the sinking crystal 4 times, the 0.5～2.0mm that at every turn sinks, and the temperature variations of looking each after the sinking carries out temperature adjustment, tends to balance until temperature; The deviation range that is the diameter before the conversion of crystal diameter and crystal interface is in ± the 0.5mm.
F. change auto state over to, crystal begins plane interface growth; The controlled step of its auto state is: the fs, and crystalline style rotating speed 45rpm, crystal plane interface growth length 30mm, the crystalline style pull rate is increased to 3.5mm/h from the zero line increase always; Subordinate phase, crystalline style rotating speed are 45rpm, crystal plane interface growth length 50mm, pull rate 3.5mm/h; Phase III, the crystalline style rotating speed is reduced to 30rpm from the 45rpm linearity of subordinate phase, crystal plane interface growth length 40mm, and pull rate reduces near always 2.0mm/h from the 3.5mm/h of subordinate phase is linear.
Growth ending, on shake crystal 8mm, slowly be cooled to room temperature, take out crystal.
The crystal perfection that present embodiment grows is transparent, and uniform internal stress is not observed scattering and dislocation.The crystalline lattice parameter is
The variation of whole crystalline lattice parameter less than
Embodiment 7:
A kind of preparation method of gadolinium gallium garnet planar interface crystal, by following mole proportioning,
Feed molar (mol)
Gd
2O
3 3(1-x/3)
Ga
2O
3 5(1.02-y/5-z/5)
CaO 2x
MgO 2y
ZrO
2 2z
Choose x=0.75, y=0.75, z=1.50.
Gd by said ratio weighing purity 4.5N
2O
3, Ga
2O
3And analytically pure CaO, ZrO
2, uniform mixing, compression moulding, 1300 ℃ of sintering 15 hours, the single crystal growing furnace of packing into is evacuated to furnace pressure≤10Pa, charges into argon gas, is heated to the raw material fusing, charges into oxygen (intrinsic standoff ratio of oxygen and argon gas is 5: 95), the unlatching gas flow means.It is 12rpm that the crystalline style rotating speed is set, pull rate is 0.5mm/h, crystal automatic seeding shouldering in single crystal growing furnace is also changeed shoulder and is changed isometrical protruding interface growth (crystal diameter Φ 51mm) over to, when the protruding interface of crystal isodiametric growth to 30mm length comes into effect Artificial Control interface conversion process:
A. stop to lift, promptly the crystal pulling rate is reduced to zero;
B. pre-temperature adjustment, its temperature adjustment amplitude is at-100 ℃;
C. rotating speed: 50rpm resets;
D. temperature adjustment, its temperature adjustment amplitude is+20 ℃;
E. divide the sinking crystal 4 times, the 0.5～1.5mm that at every turn sinks, and the temperature variations of looking each after the sinking carries out temperature adjustment, tends to balance until temperature; The deviation range that is the diameter before the conversion of crystal diameter and crystal interface is in ± the 0.5mm;
F. change auto state over to, crystal begins plane interface growth; The controlled step of its auto state is: the fs, and crystalline style rotating speed 50rpm, crystal plane interface growth length 20mm, the crystalline style pull rate is increased to 1.5mm/h from the zero line increase always; Subordinate phase, crystalline style rotating speed are 50rpm, crystal plane interface growth length 40mm, pull rate 1.5mm/h; Phase III, the crystalline style rotating speed is reduced to 30rpm from the 50rpm linearity of subordinate phase, crystal plane interface growth length 60mm, and pull rate reduces near always 0.1mm/h from the 1.5mm/h of subordinate phase is linear.
Growth ending, on shake crystal 8mm, slowly be cooled to room temperature, take out crystal.
The crystal perfection that present embodiment grows is transparent, and internal stress is better, does not observe obvious scattering and dislocation.The crystalline lattice parameter is
The variation of whole crystalline lattice parameter less than
Claims (2)
1. the preparation method of a gadolinium gallium garnet planar interface crystal, it is characterized in that: comprise following processing step: 1. raw material comprises pure gadolinium gallium garnet crystal, CaO and/or MgO, ZrO
2, the purity of each component is as follows, presses each component of following proportioning mole weighing:
Feed molar purity
Gd
2O
3 3(1-x/3) 4.5N
Ga
2O
3 5(1.02-y/5-z/5) 4.5N
CaO 2x analytical pure
MgO 2y analytical pure
ZrO
2The 2z analytical pure
Wherein, the span of x: 0～0.75mol, the span of y: 0～0.75mol, the span of z: 0.01～1.5mol;
2. load weighted each component raw material is mixed in the multilayer latex rubber bag of packing into, after cold isostatic press compression moulding, 1100～1300 ℃ of sintering temperature reactions 10～15 hours;
3. go in the single crystal growing furnace the above-mentioned material that sinters is packaged, charge into argon gas after vacuumizing, wait to expect to charge into oxygen after the heat fused, wherein, the intrinsic standoff ratio of oxygen and argon gas is (1～5): (99～95), open flow atmosphere control device then;
4. the crystalline style rotating speed is set is 8～15rpm, and pull rate is 0.5～3.5mm/h, makes crystal automatically seeding shouldering and change isometrical protruding interface growth in single crystal growing furnace; When the isodiametric growth 15～30mm of the protruding interface of crystal, change manual state over to, implement Artificial Control interface conversion process, comprise that processing step is as follows:
A. stop to lift, promptly the crystal pulling rate is reduced to zero;
B. pre-temperature adjustment, according to the difference of crystal diameter and thermal field, its temperature adjustment amplitude is in-100～+ 50 ℃ of scopes;
C. rotating speed: 15～50rpm resets;
D. temperature adjustment, its temperature adjustment amplitude are generally in-20～+ 20 ℃ of scopes;
E. divide the sinking crystal 3～4 times, the 0.5～2.0mm that at every turn sinks, and the temperature variations of looking each after the sinking carries out temperature adjustment, tends to balance until temperature;
F. change auto state over to, crystal begins plane interface growth, pull rate 0.1～5.0mm/h; The controlled step of described auto state is: the fs, the crystalline style speed range is 15～50rpm, crystal plane interface growth length range is 10～30mm, and the crystalline style pull rate is from the zero line increase, and the maximum value that this crystalline style pull rate allows to be increased to is 5.0mm/h; Subordinate phase, the rotating speed of crystalline style rotating speed and fs is identical, crystal plane interface growth length range 30～50mm, the crystalline style pull rate keeps the maximum value of fs pull rate constant; Phase III, the crystalline style rotating speed reduces from the rotating speed of subordinate phase is linear, the minimum value that this rotating speed allows to be reduced to is 15rpm, crystal plane interface growth length range is 40～60mm, pull rate reduces from the pull rate value of subordinate phase is linear, and the minimum value that this pull rate allows to be reduced to is 0.1mm/h.
5. growth ending, on shake crystal 8～15mm, slowly be cooled to room temperature, take out crystal.
2. the preparation method of a kind of gadolinium gallium garnet planar interface crystal according to claim 1 is characterized in that: the temperature of described e step tends to balance the deviation range of the crystal diameter that is meant growth and the diameter before the crystal interface conversion in ± the 0.5mm.
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| CN2008100444276A CN101319389B (en) | 2008-05-22 | 2008-05-22 | Preparation method of gadolinium gallium garnet planar interface crystal |
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| JP6500807B2 (en) * | 2016-02-25 | 2019-04-17 | 住友金属鉱山株式会社 | Growth method of CaMgZr substituted gadolinium gallium garnet (SGGG) single crystal |
| CN114164491A (en) * | 2021-11-24 | 2022-03-11 | 山东大学 | Ion-doped gadolinium-gallium garnet crystal and preparation method and application thereof |
Citations (3)
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| US4483734A (en) * | 1981-02-09 | 1984-11-20 | Shin-Etsu Chemical Co., Ltd. | Method for the preparation of single crystals of gadolinium gallium garnet |
| CN1621576A (en) * | 2004-10-13 | 2005-06-01 | 中国科学院上海光学精密机械研究所 | Growth method of neodymium-doped gadolinium gallium garnet laser crystal |
| CN1648288A (en) * | 2004-11-26 | 2005-08-03 | 中国科学院上海光学精密机械研究所 | Growing method of chromium and neodymium double doped gadolinium-gallium garnet self Q switching laser crystal |
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|---|---|---|---|---|
| US4483734A (en) * | 1981-02-09 | 1984-11-20 | Shin-Etsu Chemical Co., Ltd. | Method for the preparation of single crystals of gadolinium gallium garnet |
| CN1621576A (en) * | 2004-10-13 | 2005-06-01 | 中国科学院上海光学精密机械研究所 | Growth method of neodymium-doped gadolinium gallium garnet laser crystal |
| CN1648288A (en) * | 2004-11-26 | 2005-08-03 | 中国科学院上海光学精密机械研究所 | Growing method of chromium and neodymium double doped gadolinium-gallium garnet self Q switching laser crystal |
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| 朱化南等.GGG(Ca,Mg,Zr):(Nd,Cr)激光新晶体的生长及测试.《中国激光》.1986,第13卷(第11期),710-713. * |
| 陶德节等.提拉法生长钆镓石榴石(GGG)晶体.《量子电子学报》.2003,第20卷(第5期),550-552. * |
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