CN101723435A - Zinc oxide crystals and preparation method thereof - Google Patents
Zinc oxide crystals and preparation method thereof Download PDFInfo
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- CN101723435A CN101723435A CN200810073861A CN200810073861A CN101723435A CN 101723435 A CN101723435 A CN 101723435A CN 200810073861 A CN200810073861 A CN 200810073861A CN 200810073861 A CN200810073861 A CN 200810073861A CN 101723435 A CN101723435 A CN 101723435A
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Abstract
The invention relates to scandium-doped zinc oxide (Sc:ZnO) crystals and a preparation method thereof. In the invention, a small amount of scandium (Sc) is added in the preparation of ZnO to effectively improve the growing speed of an m plane and make quick growing of large-size ZnO crystals possible; the shapes of the crystals are reasonably changed to improve the growing efficiency of the crystals; usually, the ZnO crystals grow in hexagonal pyramid shapes, but after being doped with the scandium, the crystals grow in hexagonal prism shapes while keeping the +c slice area available above a +c region constant; and after scandium doping, the phenomenon that twin crystals are likely to develop in the growing process of the ZnO crystals and other phenomena are improved. Compared with the prior art, the grown Zinc oxide single crystals have the characteristics of high growing speed (particularly on the m plane), high growing efficiency, high crystal quality and the like. The method has high repeatability and low cost and is applicable to batch production.
Description
(1) technical field:
The present invention relates to a kind of crystalline material, specifically a kind of zincite crystal, this material are the important substrate materials of making emitting electron devices such as zinc oxide, gan.The invention still further relates to the preparation method of zincite crystal.
(2) background technology:
Zinc oxide (ZnO) crystal causes that as a kind of wide bandgap semiconductor materials people pay close attention to greatly in recent years.Existing a plurality of research groups have successively reported based on the P type doping of ZnO, the electroluminescent of zno-based LED and the ultraviolet detector of zno-based.Because the exciton bind energy of ZnO is big, low, the tunable bandwidth wide ranges of pumping threshold under the room temperature, than being easier to cleavage (with respect to α-Al
2O
3Deng) etc. good performance, ZnO will be expected to be widely used at the aspects such as substrate of ultraviolet, blue light LD and LED, hetero epitaxy and iso-epitaxy PN junction, the energy limiter of high peak energies, the high-quality gan of major diameter (GaN) from now on.Particularly in a single day the LED of zno-based, LD enter the commercial applications stage, and then the market requirement to the iso-epitaxy substrate of zno-based will be huge.
Usually large scale ZnO crystalline growth method has: hydrothermal method, flux method, CVT method, pressurized melt method etc.Owing to easily distil under the ZnO high temperature and have higher vapour pressure, be generally used for growing large-size crystalline traditional method, be to grow ZnO body monocrystalline as melt crystal pulling method etc.; Flux method can only obtain the less crystal of size now, and poor quality; Reach ZnO crystal more than 2 inches though CVT method and pressurized melt method can obtain diameter, crystal growing process is difficult to control, and the crystalline defective is more, and quality is not as the crystal of Hydrothermal Growth.
Because ZnO is a kind of polar crystal, crystal presents significant anisotropism when adopting the growth of hydrothermal method or flux method, as shown in Figure 1, the crystal face that mainly appears has+c face ((0001) face) ,-the c face (
Face), the m face (
Face family), the p face (
Face family) etc.Generally+and c looks unfamiliar long fastestly, and the speed of growth of other crystal faces is all very little, and the speed of growth of particularly parallel with c direction of principal axis m face is the slowest, and the very unfavorable and crystal of this ZnO crystal to growing large-size easily develops into the hexagonal pyramid shape.In addition because the ZnO crystal polar growth, crystal-c zone (i.e. edge-c look unfamiliar long zone) foreign matter content height, of poor quality, crystal only+the c zone has practical value.So just make: the crystal that 1. is not easy to obtain big+c section; 2. available on crystal+c zone+c section area is more and more littler.
(3) summary of the invention:
The present invention will disclose a kind of zincite crystal and preparation method thereof.
The present invention mixes a spot of scandium element (Sc) when the preparation ZnO crystal, grow zinc oxide (Sc:ZnO) crystal of mixing scandium.
In that preparation is described by the present invention when mixing scandium zinc oxide (Sc:ZnO) crystal, preferably adopt a kind of in hydrothermal method, flux method, CVD method, the pressurized melt method, can certainly adopt the additive method of existing preparation zincite crystal, just different with existing method is to add scandium element (Sc) in preparation process.
The adding of scandium element (Sc) can be selected different reagent as required, contains SC but be preferably to use
2O
3Reagent.
The joining day of scandium element (Sc), it can be preparatory stage at raw material, as adopt the pressurized melt method to prepare when mixing scandium zinc oxide (Sc:ZnO) crystal, generally be to add the reagent that contains scandium element (Sc) in the raw material preparatory stage, for example will contain the SC2O3 powder reagent and add in the raw material and mix, mix scandium zinc oxide (Sc:ZnO) crystal can preparing then by the pressurized melt method.The joining day of scandium element (Sc), other stages that also can be in the crystal preparation process when adopting Hydrothermal Preparation to go out to mix scandium zinc oxide (Sc:ZnO) crystal, are together to put into reactor at reagent and other raw materials that when filling with substance will contain scandium element (Sc).
Scandium zinc oxide (Sc:ZnO) crystal of mixing of the above generation mainly is meant and mixes scandium zinc oxide (Sc:ZnO) body monocrystalline.
Detect scandium zinc oxide (Sc:ZnO) crystal of mixing of the present invention with ICP, the weight of Scium trioxide wherein generally accounts for more than 0.0001% of crystal gross weight; The weight that is preferably Scium trioxide wherein accounts for 0.001～3% of crystal gross weight.
The present invention is by mixing an amount of scandium (Sc) element in crystal growing process, thereby reaches the problem that exists when solving above-mentioned growth ZnO crystal, mainly can reach following purpose:
Improve the speed of growth of m face effectively, for quick growing large-size ZnO crystal provides possibility: (under the Hydrothermal Growth condition) generally speaking, the speed of growth of zincite crystal m face is that 1mm/ is about the month, mix that the speed of growth of crystal m face is increased to 3-4mm/ about the month behind the scandium, and the speed of growth of crystal+c face does not have substantially to change.
Rationally change the crystalline pattern, improve growing efficiency: generally, ZnO crystal can develop into the hexagonal pyramid shape, can make that so available+c section area is more and more littler on crystal+c zone.After mixing the scandium element, change has taken place in the crystalline growth morphology, and crystal development becomes six prismatic (see figure 2)s, kept+available on the c zone+c section area do not change.
Help to improve the crystalline quality: generally be prone to twin in the ZnO crystal process of growth than phenomenons such as growths, the crystalline quality is destroyed.After mixing the scandium element in the process of growth, this phenomenon is inhibited, and crystal mass improves.
The present invention compares with technology formerly, and the zinc oxide body monocrystalline of being grown has characteristics such as fast growth (particularly m face direction), growth efficiency height, crystal mass be good, and good reproducibility, and cost is low, is applicable to batch process.
(4) description of drawings:
Gained zincite crystal shape synoptic diagram when Fig. 1 adopts hydrothermal method or flux method growth for having now.
Fig. 2 scandium zinc oxide (Sc:ZnO) crystal shape synoptic diagram of mixing of the present invention.
Fig. 3 is that the present invention mixes the used growing apparatus diagrammatic cross-section of a kind of embodiment of scandium zinc oxide (Sc:ZnO) crystalline with Hydrothermal Growth.
The accompanying drawing sign:
1, zincite crystal+c face ((0001) face); 2, zincite crystal-the c face (
Face); 3, the m face of zincite crystal (
Face family); 4, the p face of zincite crystal (
Face family); 5, autoclave kettle; 6, gold lining pipe; 7, baffle plate; 8, culture material; 9, dissolve area; 10, vitellarium; 11, seed crystal frame: 12, seed wafer.
(5) embodiment:
Be example explanation the specific embodiment of the present invention below with the hydrothermal method.
Present embodiment has adopted growing apparatus shown in Figure 3, this device uses autoclave and supporting with it temperature difference well formula resistance furnace to form, be provided with gold lining pipe 6 in the autoclave kettle 5, gold lining pipe 6 inner cavity size Φ 38mm * 750mm in this embodiment, thickness of pipe 0.8mm.
This employing hydrothermal method is synthesized the Sc:ZnO crystal, and gold lining pipe 6 inner chambers have the mixing solutions of mineralizer and H2O, the ceramic body raw material that is sintered into by the ZnO powder and contain Sc
2O
3The culture material of forming 8 is positioned at the bottom (dissolve area just) of gold lining pipe 6 inner chambers, and baffle plate with holes 7 is arranged at culture material 8 tops, and baffle plate 7 is divided into 10 two parts of dissolve area 9 and vitellarium with gold lining pipe 6.Also be provided with trapezoidal seed crystal frame 11 in the gold lining pipe 6, seed crystal frame 11 is positioned at top (vitellarium just) of gold lining pipe 6 tops, baffle plate 7.The seed wafer 12 that cuts is fixed on the seed crystal frame 11.Seed wafer 12 needs by certain direction cutting, and the cut direction of general ZnO seed wafer 12 is (0001) direction.
The present invention's Sc:ZnO crystalline step of growing is as follows:
400 gram particles are directly put into the dissolve area 9 of gold lining pipe 6 bottoms for the ZnO powder sintering piece of 2-8mm, 1 gram Sc2O3 powder or powder agglomerate.
Distinguish the different schemes preparation mineralizer of according to the form below and the mixing solutions of water again, the compactedness by 70%, 78%, 85% adds the mixing solutions of mineralizer 7 and water.
The mineralizer solution and the compactedness of table 1 different schemes
| The scheme numbering | Mineralizer concentration | Compactedness |
| ??1 | ??1.0mol/L?KOH+0.5mol/L??LiOH+1％H 2O | ??70％ |
| ??2 | ??3.0mol/L?KOH+0.5mol/L??LiOH+1％H 2O | ??78％ |
| ??3 | ??2.0mol/L?KOH+1.0mol/L??LiOH+1％H 2O | ??85％ |
| ??4 | ??2.0mol/L?KOH+0.5mol/L??LiOH+1％H 2O | ??70％ |
| ??5 | ??3.0mol/L?KOH+1.0mol/L??LiOH+1％H 2O | ??78％ |
| ??6 | ??3.0mol/L?KOH+0.5mol/L??LiOH+1％H 2O | ??85％ |
The trapezoidal seed crystal frame 11 that uses the gold silk to make, the ZnO seed wafer 12 two ends polishing of 30 * 30 * 1mm that cuts by (0001) direction spiles at the edge, connects aperture with the gold silk, and is fixed on the seed crystal frame 11.
Resistance furnace heats up, and adjusts temperature and pressure.Dissolve area 9 temperature are 280-400 ℃, and vitellarium 10 temperature are 260-390 ℃, temperature difference 10-20 ℃; Operating pressure 1100atm; In the 10 ℃/h of heat-up rate, the autoclave internal and external temperature reaches balance, and the constant temperature growth is 30 days under this temperature.
Stay-warm case is opened in cooling, blowing out, and autoclave proposes burner hearth, takes out crystal block, and crystal is sparkling and crystal-clear transparent, and the nothing cotton does not have to be split, and integrity is good.Crystal boundary is hexa-prism as shown in Figure 2.
Adopt ICP to detect to the new grown layer of crystal, the weight of Scium trioxide wherein accounts for 0.001% of crystal gross weight.
The gained crystal by (0001) section polishing, be can be used as ZnO or InN-GaN substrate material.
Claims (8)
1. zincite crystal, it is characterized in that: described zincite crystal is a zincite crystal of mixing scandium.
2. zincite crystal according to claim 1 is characterized in that: more than 0.0001%.
3. zincite crystal according to claim 2 is characterized in that: the weight of the Scium trioxide in the zincite crystal accounts for 0.001～3% of crystal gross weight.
4. zincite crystal according to claim 1 is characterized in that: described zincite crystal is a zinc oxide body monocrystalline.
5. the preparation method of zincite crystal, it is characterized by this method is to mix scandium in preparation ZnO crystal process.
6. the preparation method of zincite crystal according to claim 5, it is characterized by zincite crystal is zinc oxide body monocrystalline.
7. the preparation method of zincite crystal according to claim 5, the synthetic method that it is characterized by described zincite crystal are a kind of in hydrothermal method, flux method, CVD method, the pressurized melt method.
8. the preparation method of zincite crystal according to claim 5 is characterized by to be to use and contains Sc
2O
3Reagent is mixed scandium when the growth ZnO crystal.
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| CN200810073861A CN101723435A (en) | 2008-10-24 | 2008-10-24 | Zinc oxide crystals and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105297134A (en) * | 2015-11-10 | 2016-02-03 | 中国有色桂林矿产地质研究院有限公司 | Gallium and scandium co-doping zinc oxide scintillation single crystal and preparation method thereof |
| CN113184895A (en) * | 2021-04-23 | 2021-07-30 | 西安交通大学 | Controllable double-layer prismatic-disk-shaped micron zinc oxide and preparation method thereof |
-
2008
- 2008-10-24 CN CN200810073861A patent/CN101723435A/en active Pending
Non-Patent Citations (1)
| Title |
|---|
| SHAO-MIN ZHOU ET AL.: "Preparation and photoluminescence of Sc-doped ZnO nanowires", 《PHYSICA E》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105297134A (en) * | 2015-11-10 | 2016-02-03 | 中国有色桂林矿产地质研究院有限公司 | Gallium and scandium co-doping zinc oxide scintillation single crystal and preparation method thereof |
| CN113184895A (en) * | 2021-04-23 | 2021-07-30 | 西安交通大学 | Controllable double-layer prismatic-disk-shaped micron zinc oxide and preparation method thereof |
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Application publication date: 20100609 |