CN102352527A - Method for growing zinc oxide crystals through induction heating and pressure - Google Patents
Method for growing zinc oxide crystals through induction heating and pressure Download PDFInfo
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- CN102352527A CN102352527A CN2011103299609A CN201110329960A CN102352527A CN 102352527 A CN102352527 A CN 102352527A CN 2011103299609 A CN2011103299609 A CN 2011103299609A CN 201110329960 A CN201110329960 A CN 201110329960A CN 102352527 A CN102352527 A CN 102352527A
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Abstract
The invention discloses a method for growing zinc oxide crystals through induction heating and pressure, which adopts a induction heating and pressure crystal growing device and comprises the following steps: heating a zinc oxide raw material in a crucible to melt, and slowly cooling to lead the melt to gradually crystallize along the seed crystals and ensure crystal growth is completed. By adjusting an induction coil and a heat insulating material, the temperature field gradient of the device can be adjusted to 20-80 DEG C/cm. The temperature is adjusted in a cooling rate of 1-20 DEG C/h in the crystal growing process, the temperature is adjusted in a cooling rate of 20-100 DEG C/h after crystal growth, and the crystals are cooled to the room temperature along with the furnace after a power supply is powered off. The method has the advantages that the temperature field and crystal growth interface are stable, the growth pressure is low (less than 4MPa), the growth period is short, the crystal purity is high, and the growing device is simple and is convenient and easy to control; ZnO crystals with high purity and low defect can be grown; and the quality requirement on the epitaxial growth of high-quality ZnO films on a substrate can be met.
Description
Technical field
The present invention relates to the growth method of zincite crystal, specifically is the method that in induction heating pressure crystal growing apparatus, adopts the terraced method growth of Frequency Induction Heating pressure temperature ZnO crystal.
Background technology
In recent years, based on the realization of ultraviolet laser, ZnO has become one of research focus of field of semiconductor materials.Compare SiC, other wide bandgap materials such as GaN, ZnO have the characteristics of aboundresources, cheap and good stability.The ZnO monocrystalline is a kind of multi-functional crystal with performances such as semi-conductor, luminous, piezoelectricity, electric light, flickers, is about to become photoelectron material of future generation, has quite wide application prospect.Moreover, in order to study the semiconducting behavior of zinc oxide better, also must synthetic high-quality zinc oxide body monocrystalline.But because its fusing point is up to 1975 ℃, at high temperature (more than 1400 ℃) distillation phenomenon is serious, also has intensive polarity crystallization characteristic, so this crystal growth difficulty very.As far back as the sixties in 20th century, people just begin to pay close attention to the growth of ZnO monocrystalline, although attempted a variety of growth techniques, the crystalline size of gained is all very little, generally in the millimeter magnitude, does not have practical value.In view of there is very big difficulty in bulk growth, people turn on attention the increment study of ZnO film gradually, are once once treating coldly the exploration to bulk growth technology.Recently, along with GaN, developing rapidly of novel photoelectric material industries such as SiC, also increasing to the demand of high quality, large-sized ZnO monocrystal chip, the increment study of ZnO body monocrystalline just causes scientist's attention again.
Both at home and abroad mainly with Hydrothermal Preparation large scale ZnO crystal, have the lithium and the sodium of higher concentration in the ZnO crystal of Hydrothermal Preparation at present, these impurity can be diffused in the ZnO film in thin film growth process, thereby reduce the crystalline quality of film.
Summary of the invention
The method that the purpose of this invention is to provide a kind of induction heating pressure developing zinc oxide crystallite comprises an induction heating pressure crystal growing apparatus.This method has that temperature is stablized with crystal growth interface, growth pressure low (＜4MPa), growth cycle is short, crystal purity is high, growing apparatus is easy and be easy to advantage such as control; Can grow the ZnO crystal of high purity, low defective, satisfy the specification of quality of the high-quality ZnO film of epitaxy substrate.
Technical solution of the present invention is following:
The method of the terraced method developing zinc oxide crystallite of a kind of induction heating pressure temperature comprises an induction heating pressure crystal growing apparatus, and its characteristics are: be filled with the CO that pressure is 1～4MPa in the crystal growing process in the burner hearth
2With Ar or (N
2Mixed gas, CO wherein
2Shared volume ratio is 2%～15%, and the mode through the Medium frequency induction Iridium Crucible heats; Iridium Crucible is taper, and the tapered section head is placed with seed crystal, and there is water-cooled iraurite cushion block the seed crystal lower end; The crucible tapered section places the zirconium white insulated tank, and the outer alumina hollow ball of filling, the peripheral zirconia powder of filling of crucible equal-diameter part are as thermal insulation layer, and the outer quartz tube of using of zirconia powder is fixed; Locate to be connected with respectively thermopair at seed crystal and melt etc., can detection at any time temperature conditions everywhere; Crude zinc oxide materials is to fusing in the heating crucible, and slowly cooling makes melt along slowly crystallization of seed crystal again, until accomplishing crystal growth.
The method of described induction heating pressure developing zinc oxide crystallite is to be higher than 6 * 10 being evacuated to vacuum tightness
-2Behind the Pa, be filled with the CO that pressure is about 1～4MPa
2And Ar (N
2) mixed gas (CO
2Shared volume ratio is 2%～15%) adopt the mode growing crystal of the terraced method of induction heating pressure temperature under the condition.Through regulating warm field gradient that thermal source such as ruhmkorff coil, zirconium white insulated tank, zirconia powder and alumina hollow ball and lagging material make this device in 20-80 ℃/cm atmosphere; The crystal growing process rate of temperature fall is 1-20 ℃/hour, and rate of temperature fall is that 20-100 ℃ of/hour cooling rate reduced to 200 ℃ behind the growth ending, and powered-down cools to room temperature with the furnace, takes out crystal.
Technique effect of the present invention:
Compare with traditional method, directly inductive crucible heating improves heating efficiency greatly; Can adjust the suitable temp gradient according to the size of regulating ruhmkorff coil, position and lagging material relation; Optimize problem restive with crystal solid-liquid interface place thermograde in the melt method for growing zincite crystal process and adjusting, be beneficial to the automatization control that realizes crystal growth.Adopt the induction heating method growing crystal, heat-insulation system makes simply, not yielding, and cost is relatively low, and is low relatively slightly to power supply and stove performance requriements, and whole cost reduces.
The inventive method has overcome and has existed in the ZnO crystal of Hydrothermal Preparation than high impurity concentration, growth cycle is long, growth pressure is high shortcomings such as (120MPa); Have that temperature is stablized with crystal growth interface, growth pressure low (＜4MPa), growth cycle is short, crystal purity is high, growing apparatus is easy and be easy to advantage such as control; Can grow the ZnO crystal of high purity, low defective, satisfy the specification of quality of the high-quality ZnO film of epitaxy substrate.
Description of drawings
The gradient furnace structural representation that Fig. 1 uses for induction heating pressure developing zinc oxide crystallite of the present invention
Embodiment
Below in conjunction with embodiment and accompanying drawing the present invention is described further, but should limit protection scope of the present invention with this.
Embodiment 1: the zincite crystal that adopts method growth diameter Φ 30 of the present invention
At first; Through regulating the size of ruhmkorff coil; Position and lagging material relation; Making the thermograde of this device temperature field is 20 ℃/cm; In crude zinc oxide materials and seed crystal (seed crystal direction the be 0001 to) Iridium Crucible of packing into; And by the induction heater that installs shown in Figure 1, among the figure: 1-stainless steel body of heater; The 2-quartz tube; The 3-ruhmkorff coil; The 4-zirconium is husky; The 5-Iridium Crucible; 6 melts; The 7-seed crystal; 8 alumina plates; The 9-tetrafluoroethylene; The 10-bolt of lower base; 11-Iridium Crucible lid; 12-zirconium white insulation cover; The thick hot device of 13-; The 14-coil brace; The 15-alumina hollow ball; 16-zirconium white insulated tank; 17-iraurite piece; 18-tetrafluoroethylene bolt; 19-seed crystal water-cooled tube; The 20-thermopair.Be evacuated to vacuum tightness and be better than 6 * 10
-2Pa, charged pressure are the CO of 4MPa
2With Ar or (N
2Mixed gas (CO wherein
2Shared volume ratio is 2%) after begin to heat up raw material melted; Through observing the temperature conditions of thermopair; Adjust suitable rate of temperature fall; Cooling rate cooling growing crystal with 1 ℃/hour; Crystal growth finishes the back and reduces to 200 ℃ with 100 ℃/hour cooling rate; Powered-down cools to room temperature with the furnace, takes out crystal.Growing crystalline size is Φ 30 * 50mm
3Zincite crystal.
Embodiment 2: adopt method growth Φ 30 zincite crystals of the present invention
At first; Making the thermograde of this device temperature field through size, position and the lagging material relation of regulating ruhmkorff coil is 30 ℃/cm; In crude zinc oxide materials and seed crystal (seed crystal direction the be 0001 to) Iridium Crucible of packing into; And, be evacuated to vacuum tightness and be higher than 6 * 10 by the induction heater that installs shown in Figure 1
-2Pa, charged pressure are the CO of 1.5MPa
2And Ar (N
2) mixed gas (CO wherein
2Shared volume ratio is 5%) after begin to heat up raw material melted; Through observing the temperature conditions of thermopair; Adjust suitable rate of temperature fall; Cooling rate cooling growing crystal with 20 ℃/hour; Crystal growth finishes the back and reduces to 200 ℃ with 80 ℃/hour cooling rate; Powered-down cools to room temperature with the furnace, takes out crystal.Growing crystalline size is Φ 30 * 50mm
3Zincite crystal.
Embodiment 3: adopt method growth Φ 35 zincite crystals of the present invention
At first; Making the thermograde of this device temperature field through size, position and the lagging material relation of regulating ruhmkorff coil is 80 ℃/cm; In crude zinc oxide materials and seed crystal (seed crystal direction the be 0001 to) Iridium Crucible of packing into; And, be evacuated to vacuum tightness and be higher than 6 * 10 by the induction heater that installs shown in Figure 1
-2Pa, charged pressure are lower than the CO of 4MPa
2And Ar (N
2) mixed gas (CO wherein
2Shared volume ratio is 15%) after begin to heat up raw material melted; Through observing the temperature conditions of thermopair; Adjust suitable rate of temperature fall; Cooling rate cooling growing crystal with 10 ℃/hour; Crystal growth finishes the back and reduces to 200 ℃ with 20 ℃/hour cooling rate; Powered-down cools to room temperature with the furnace, takes out crystal.Growing crystalline size is Φ 35 * 50mm
3Zincite crystal.
Embodiment 4: adopt method growth Φ 35 zincite crystals of the present invention
At first; Making the thermograde of this device temperature field through size, position and the lagging material relation of regulating ruhmkorff coil is 40 ℃/cm; In crude zinc oxide materials and seed crystal (seed crystal direction the be 0001 to) Iridium Crucible of packing into; And, be evacuated to vacuum tightness and be higher than 6 * 10 by the induction heater that installs shown in Figure 1
-2Pa, charged pressure are lower than the CO of 3MPa
2And Ar (N
2) mixed gas (CO wherein
2Shared volume ratio is 8%) after begin to heat up raw material melted; Through observing the temperature conditions of thermopair; Adjust suitable rate of temperature fall; Cooling rate cooling growing crystal with 15 ℃/hour; Crystal growth finishes the back and reduces to 200 ℃ with 80 ℃/hour cooling rate; Powered-down cools to room temperature with the furnace, takes out crystal.Growing crystalline size is Φ 35 * 50mm
3Zincite crystal.
Embodiment 5: adopt method growth Φ 40 zincite crystals of the present invention
At first; Making the thermograde of this device temperature field through size, position and the lagging material relation of regulating ruhmkorff coil is 50 ℃/cm; In crude zinc oxide materials and seed crystal (seed crystal direction the be 0001 to) Iridium Crucible of packing into; And, be evacuated to vacuum tightness and be higher than 6 * 10 by the induction heater that installs shown in Figure 1
-2Pa, charged pressure are lower than the CO of 2.5MPa
2And Ar (N
2) mixed gas (CO wherein
2Shared volume ratio is 12%) after begin to heat up raw material melted; Through observing the temperature conditions of thermopair; Adjust suitable rate of temperature fall; Cooling rate cooling growing crystal with 5 ℃/hour; Crystal growth finishes the back and reduces to 200 ℃ with 60 ℃/hour cooling rate; Powered-down cools to room temperature with the furnace, takes out crystal.Growing crystalline size is Φ 40 * 50mm
3Zincite crystal.
Embodiment 6: adopt method growth Φ 40 zincite crystals of the present invention
At first; Making the thermograde of this device temperature field through size, position and the lagging material relation of regulating ruhmkorff coil is 35 ℃/cm; In crude zinc oxide materials and seed crystal (seed crystal direction the be 0001 to) Iridium Crucible of packing into; And, be evacuated to vacuum tightness and be higher than 6 * 10 by the induction heater that installs shown in Figure 1
-2Pa, charged pressure are lower than the CO of 3.5MPa
2And Ar (N
2) mixed gas (CO wherein
2Shared volume ratio is 7%) after begin to heat up raw material melted; Through observing the temperature conditions of thermopair; Adjust suitable rate of temperature fall; Cooling rate cooling growing crystal with 8 ℃/hour; Crystal growth finishes the back and reduces to 200 ℃ with 100 ℃/hour cooling rate; Powered-down cools to room temperature with the furnace, takes out crystal.Growing crystalline size is Φ 40 * 50mm
3Zincite crystal.
Experiment shows; The present invention can be in lower power consumption; Grow the large size high quality zinc oxide crystal under the lower cost; Can regulate the suitable temp gradient according to the size of regulating ruhmkorff coil, position and lagging material relation; Optimize problem restive with crystal solid-liquid interface place thermograde in the melt method for growing zincite crystal process and adjusting, be beneficial to the automatization control that realizes crystal growth.And heating and heat-insulation system are made simply, not yielding, warm field is stable, can life-time service.
Claims (1)
1. the method for an induction heating developing zinc oxide crystallite adopts induction heating pressure gradient furnace to grow, and its characteristics are:
In crude zinc oxide materials and seed crystal (seed crystal direction the be 0001 to) Iridium Crucible of packing into, be evacuated to vacuum tightness and be higher than 6 * 10
-2Behind the Pa, be filled with the CO that pressure is 1～4MPa in the crystal growing process in the burner hearth
2With Ar or N
2Mixed gas, CO wherein
2Shared volume ratio is 2%～15%, through Frequency Induction Heating Iridium Crucible (5); Iridium Crucible (5) is placed with seed crystal (7) for round shape awl bottom structure at the awl end, and there is water-cooled iraurite cushion block (17) the seed crystal lower end; Be placed in bottom Iridium Crucible (5) awl in the zirconium white insulated tank (16), skin is filled alumina hollow ball (15), and zirconia powder (4) is filled as thermal insulation layer in the periphery of the cylinder of Iridium Crucible (5), and zirconia powder (4) outer use quartz tube (2) is fixed; Locate to be connected to respectively thermopair (20) at seed crystal and melt (4), can detection at any time temperature conditions everywhere;
Through regulating warm field gradient that ruhmkorff coil, zirconium white insulated tank, zirconium sand and alumina hollow ball make this device in 20～80 ℃/cm atmosphere;
Crude zinc oxide materials is to fusing in the heating crucible; The crystal growing process rate of temperature fall is 1～20 ℃/hour; Make melt along upwards slowly crystallization of seed crystal; Until accomplishing crystal growth; Be that 20～100 ℃ of/hour cooling rates are reduced to 200 ℃ with speed behind the growth ending; Powered-down cools to room temperature with the furnace, takes out crystal.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102703973A (en) * | 2012-06-05 | 2012-10-03 | 西安理工大学 | Method for growing zinc oxide crystal |
| CN102703972A (en) * | 2012-06-05 | 2012-10-03 | 西安理工大学 | Device for growing zinc oxide crystal |
| CN107541776A (en) * | 2017-08-14 | 2018-01-05 | 同济大学 | A kind of growth apparatus and method of large scale gallium oxide single crystal |
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| US5131975A (en) * | 1990-07-10 | 1992-07-21 | The Regents Of The University Of California | Controlled growth of semiconductor crystals |
| CN101384756A (en) * | 2006-03-01 | 2009-03-11 | 三菱瓦斯化学株式会社 | Process for producing zno single crystal according to method of liquid phase growth |
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2011
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Patent Citations (2)
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| US5131975A (en) * | 1990-07-10 | 1992-07-21 | The Regents Of The University Of California | Controlled growth of semiconductor crystals |
| CN101384756A (en) * | 2006-03-01 | 2009-03-11 | 三菱瓦斯化学株式会社 | Process for producing zno single crystal according to method of liquid phase growth |
Non-Patent Citations (5)
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102703973A (en) * | 2012-06-05 | 2012-10-03 | 西安理工大学 | Method for growing zinc oxide crystal |
| CN102703972A (en) * | 2012-06-05 | 2012-10-03 | 西安理工大学 | Device for growing zinc oxide crystal |
| CN102703973B (en) * | 2012-06-05 | 2015-03-25 | 西安理工大学 | Method for growing zinc oxide crystal |
| CN107541776A (en) * | 2017-08-14 | 2018-01-05 | 同济大学 | A kind of growth apparatus and method of large scale gallium oxide single crystal |
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Application publication date: 20120215 |