CN102127802B - Method for growing zinc oxide monocrystalline under hydrothermal condition by utilizing mineralizer - Google Patents
Method for growing zinc oxide monocrystalline under hydrothermal condition by utilizing mineralizer Download PDFInfo
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- CN102127802B CN102127802B CN 201110066466 CN201110066466A CN102127802B CN 102127802 B CN102127802 B CN 102127802B CN 201110066466 CN201110066466 CN 201110066466 CN 201110066466 A CN201110066466 A CN 201110066466A CN 102127802 B CN102127802 B CN 102127802B
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Abstract
The invention relates to a method for growing a zinc oxide monocrystalline under a hydrothermal condition by utilizing a mineralizer. By taking zinc oxide or zinc hydroxide as raw materials for crystal growth, chloride salt as the mineralizer and deionized water as a growing solvent, crystal growth is performed in a high pressure hydro-thermal reaction kettle under different pH values. With the method provided by the invention, the growth speed of a zinc oxide monocrystalline is high, a simple process and low cost are realized, zinc oxide monocrystallines with different sizes can be obtained through controlling the process condition.
Description
Technical field
The present invention relates to a kind of method of utilizing mineralizer developing zinc oxide monocrystalline under hydrothermal condition, belong to the crystalline material field.
Background technology
Zinc oxide is a kind of important broad-band gap II-VI group iii v compound semiconductor material, have the characteristics such as the electronic migration saturation rate is high, specific inductivity is little, Heat stability is good, to make blue, green luminescence device, the candidate material of radioprotective, high frequency, high-power and High Density Integration electron device; At photoelectric field, zinc oxide can also be applied to the collection optics such as solar cell, color sensor; In the piezoelectricity field, zinc oxide can be applied to piezoelectricity conversion and senser element.In addition, because nanotechnology is flourish, coupling effect between the various character of zinc oxide is so that it can also be applied to the fields such as piezoelectron, transparent electronics, as making nano photoelectronic devices, nano generator, microelectromechanical systems (MEMS) etc.; The zinc oxide that mixes also has important application in the spintronics field.
The synthetic of Zinc oxide single crystal mainly is to adopt following three kinds of methods: flux method, chemical vapor transportation method and hydrothermal method.In these three kinds of methods, the synthetic crystal of hydrothermal method has the characteristics such as purity is high, defective is few, thermal stresses is little, quality is good, and the crystal growth rate of this synthetic method is also larger, thereby becomes the main stream approach of people's developing zinc oxide monocrystalline.The people such as Muscovite L.N.Dem ' yanets are in the autoclave take titanium alloy as liner, with KOH (3.5mol/l), LiOH (0.5～1mol/l) and NH
3H
2(0.5～1mol/l) the ZnO briquetting for mineralizer, sintering is precursor to O, and Hydrothermal Synthesis goes out the Zinc oxide single crystal that diameter reaches 3 inches, consults L.N.Dem ' yanets, V.I.Lyutin.Journal of Crystal Growth, 2008,310,993-999.CN1598076A (CN200410009367.6) discloses a kind of method with Hydrothermal Growth Zinc oxide single crystal body, it is characterized in that with zinc hydroxide as precursor, put it in the deionized water, make mineralizer with ammoniacal liquor, pH value in the hydrothermal solution is modulated to＞11, then add in the reaction autoclave, in autoclave, be heated to 100 ℃～400 ℃ of differing tempss, constant temperature time is 1 hour～40 days, carries out the growth of Zinc oxide single crystal body.The application quotes the full text of this document as prior art.
Japan the people such as T.Fukuda take platinum (Pt) in the autoclave of liner, ZnO briquetting take LiOH (1mol/l) and KOH (3.5mol/l) as mineralizer, sintering is as precursor, it is zincite crystal more than 2 inches that Hydrothermal Synthesis goes out diameter, consult K.Maeda, M.Sato, I.Niikura and T.Fukuda.Semiconductor Science and Technology.2005,20, S49-S54.The Guilin geological and mineral research institute (C.L.Zhang of China, W.N.Zhou, Y.Hang et al.Journalof Crystal Growth, 2008,310,1819-1822) and Fujian Inst. of Matter Structure, Chinese Academy of Sciences (W.W.Lin, D.G.Chen, F.Huang et al.Crystal Growth ﹠amp; Design, 2009,9,4378-4383) adopt similar mineralizer also to do a large amount of research work in this field.But owing to using traditional mineralizer (LiOH+KOH), the developing zinc oxide monocrystalline all needs to be heated to more than 300 ℃ usually under hydrothermal condition, and the supersaturated solution alkalescence that is used for the crystal growth is excessively strong, the hydrothermal reaction kettle kettle there is very strong corrodibility, so will enclose the precious metal liner at the inwall of reactor in process of growth, liner commonly used is gold (Au), platinum (Pt) and titanium alloy (Ti-Alloy).CN101748485A (CN201010100183.6) discloses a kind of preparation method of gallium-doped zinc oxide crystals, the zinc oxide culture material that will contain gallium places gold lining pipe bottom, adding a certain amount of fluorinion concentration in the gold lining pipe is the fluoride aqueous solution of 3～6mol/L, and at the top of gold lining pipe suspension seed crystal, the gold lining pipe is sealed, put into autoclave, insert sealing autoclave behind the deionized water; Afterwards autoclave is placed in the resistance furnace, making the dissolve area medial temperature is 340～430 ℃, and the vitellarium medial temperature is 330～420 ℃, through constant temperature growth in 10～90 days, obtains containing the gallium-doped zinc oxide crystals of gallium concentration between 0～15%.The application quotes the full text of this document as prior art.
Based on above technique developing zinc oxide monocrystalline high-pressure hydrothermal reaction kettle is required very highly, and the reasons such as energy consumption, fixed investment cause the zincite crystal growth cost too high, thereby have limited the application of Zinc oxide single crystal in aforementioned every field.
Summary of the invention
Too high for prior art Hydrothermal Growth Zinc oxide single crystal Heating temperature, to hydrothermal reaction kettle and substrate thereof the problem such as have relatively high expectations, the invention provides a kind of method of utilizing chloride salt mineralizer developing zinc oxide monocrystalline under hydrothermal condition.
The term explanation: " autoclave " described in the present specification, " autoclave " are synonym, all refer to hydrothermal reactor.
Technical scheme of the present invention is as follows:
A kind of under hydrothermal condition the method for developing zinc oxide monocrystalline, make the raw material of crystal growth of zinc oxide or zinc hydroxide, adding tetrafluoroethylene or argent is in the autoclave of liner, add deionized water, add the pH value of inorganic alkali solution regulator solution between 6～11, add and to contain villaumite and make mineralizer, it is 0.05～1mol/L that the add-on that control contains villaumite makes the Chlorine in Solution ionic concn;
In the solution on autoclave top, place the zinc wire and make seed crystal, the seal pot mouth; With microwave autoclave is heated, make the homo(io)thermism of autoclave at 90～100 ℃, constant temperature time is 1～2 day, gets zinc oxide crystallite; Perhaps
Place the zinc oxide seed crystal of (0001) orientation in the solution in autoclave, be heated to 150～300 ℃ of temperature, constant temperature time is 5～40 days, gets zinc oxide body piece crystal.
According to the present invention, the described villaumite that contains is selected from lithium chloride, sodium-chlor, Repone K, ammonium chloride, the zinc chloride one or more.One of preferred following combination: lithium chloride and sodium-chlor or Repone K 1: the combination of (2～5) mol ratio, zinc chloride and sodium-chlor 1: the combination of (1.5～3) mol ratio etc.
According to the present invention, the described type of heating during preferred developing zinc oxide body piece crystal is Resistant heating.Further preferred, divide upper and lower two sections autoclave heated with nickel-chromium resistance wire or nickel chromium triangle aluminium resistance wire; The Heating temperature of one group of resistance wire is higher 20～60 ℃ than top Heating temperature near one group of resistance wire of seed crystal at the bottom of the still.
According to the present invention, the compactedness of autoclave is 60%～90% to be advisable volume ratio.Mainly regulate and control by the amount that adds deionized water.
According to the present invention, the inorganic alkali solution of preferred regulator solution pH value is lithium hydroxide solution, sodium hydroxide solution or potassium hydroxide solution.
According to the present invention, preferred, add inorganic alkali solution regulator solution pH value 8～10.
According to the present invention, preferred, during the developing zinc oxide crystallite, the zinc hydroxide raw material is made suspension liquid add autoclave.
According to the present invention, preferred, during developing zinc oxide body piece crystal, with the briquetting adding autoclave base of zinc oxide or zinc hydroxide raw material.
The autoclave growth cell configuration that the inventive method is used comprises reactor, heating unit, seed crystal frame (bar), dividing plate, thermal insulation layer with liner as shown in Figure 1.Dividing plate is the middle part in reactor, reactor is divided into up and down two portions, and seed crystal and solid reaction material can be separated, and dividing plate has through hole, makes the reaction soln up/down perforation.Relevant autoclave other technologies content all can be carried out by state of the art.
Do not add detailed restriction in the inventive method, all can be with reference to the prior art of hydrothermal crystal growth.
Compared with prior art the invention has the advantages that:
1, the present invention does the raw material of crystal growth with zinc oxide or zinc hydroxide, makees mineralizer to contain villaumite, does growth solvent with deionized water, under the controllable condition of potential of hydrogen,
Under relatively low temperatureProcess
Hydro-thermalReaction
Grow growth complete, pure The zinc oxide body piece crystal that degree is good.
2, the present invention is take tetrafluoroethylene or argent as liner, gold, platinum or the titanium alloy liner that must adopt when replacing traditional high-temperature water thermal growth zinc oxide, decrease the cost of developing zinc oxide monocrystalline.
3, the growth velocity of employing the inventive method developing zinc oxide monocrystalline is fast, technique is simple, cost is low, can go out to grow the zinc oxide body piece crystal complete, that purity is good by hydrothermal growth under lower temperature; And by changing the crystal growth parameter(s)s such as reaction times, temperature, can grow the Zinc oxide single crystal of different size.
Description of drawings
The autoclave growth cell configuration schematic diagram that Fig. 1 the inventive method is used, wherein, 1, reactor, 2, well heater, 3, seed crystal (one or more), 4, dividing plate, 5, thermal insulation layer, 6, inner liner of reaction kettle, 7, growth raw material, 8, the seed crystal frame.
The zinc oxide crystallite photo of Fig. 2 embodiment of the invention 1 growth.
The zincite crystal photo of Fig. 3 embodiment of the invention 3 growths.
Embodiment
The present invention will be further described below in conjunction with drawings and Examples, but be not limited to this.Equipment therefor is prior art among the embodiment.Do not have clearly limit all can be with reference to state of the art.
Embodiment 1:
Be growth raw material with zinc hydroxide suspension, the high-temperature alloy steel that is placed on internal diameter Φ 4cm, high 9cm is made in the autoclave, and the liner of autoclave is tetrafluoroethylene.Being filled with deionized water in reactor, is mineralizer with sodium-chlor, and control Chlorine in Solution ionic concn is 0.05mol/L.Add sodium hydroxide solution the pH value in the hydrothermal solution is adjusted to 6.The compactedness that makes simultaneously autoclave is 60%.In the solution on autoclave top, place the zinc wire and make seed crystal, the seal pot mouth.With microwave autoclave is heated, make the homo(io)thermism of autoclave at 90 ℃.Be incubated 1 day, on seed crystal, can grow the ZnO crystallite.As shown in Figure 2.
Embodiment 2:
With 1 kilogram of closely knit fragment of zinc hydroxide as growth material 7, be placed at the high-temperature alloy steel of internal diameter Φ 8cm, high 0.5m and make autoclave 1 bottom, zinc hydroxide growth material top adds dividing plate 4, and the liner 6 of autoclave is tetrafluoroethylene, and autoclave has thermal insulation layer 5 outward.In reactor, be filled with deionized water, mixture (0.25mol/lZnCl2+0.5mol/l NaCl) with zinc chloride and sodium-chlor is mineralizer, add a certain amount of sodium hydroxide the pH value in the hydrothermal solution is adjusted to 9, control Chlorine in Solution ionic concn is 1mol/L.The compactedness that makes simultaneously autoclave is 80%.Behind the ZnO seed crystal 3 with seed crystal frame 8 placement (0001) orientations in the solution of autoclave top, the seal pot mouth.With upper and lower two sections of nickel-chromium resistance wire 2 minutes autoclave heated; One group of resistance wire is warmed up to 250 ℃ at the bottom of the still; Above be warmed up to 210 ℃ near one group of resistance wire of seed crystal.Be incubated 30 days, get diameter and be 3 millimeters ZnO monocrystalline.Growing apparatus as shown in Figure 1.
Embodiment 3:
As growth material, the high-temperature alloy steel that is placed on internal diameter Φ 8cm, high 0.5m is made autoclave base with 1 kilogram of closely knit briquetting of zinc oxide, and zinc oxide growth material top adds dividing plate, and the liner of autoclave is argent.Be filled with deionized water in autoclave, using the mixture (0.25mol/l LiCl+0.75mol/l NaCl) of lithium chloride and sodium-chlor is mineralizer, and adding the sodium hydroxide solution adjust pH is 10, and control Chlorine in Solution ionic concn is 1mol/L.The compactedness that makes simultaneously autoclave is 90% (volume).After in the solution of autoclave top, placing the ZnO seed crystal blocks of (0001) orientation, the seal pot mouth.Divide upper and lower two sections autoclave heated with nickel chromium triangle aluminium resistance wire; One group of resistance wire is warmed up to 280 ℃ at the bottom of the still; Above be warmed up to 230 ℃ near one group of resistance wire of seed crystal.Be incubated 38 days, get diameter and be 8 millimeters ZnO monocrystalline.As shown in Figure 3.
Embodiment 4:
As growth material, the high-temperature alloy steel that is placed on internal diameter Φ 10cm, high 2m is made autoclave base with 3 kilograms of closely knit briquettings of zinc oxide, and zinc oxide growth material top adds dividing plate, and the liner of autoclave is tetrafluoroethylene.Be filled with deionized water in reactor, using the mixture (0.25mol/l LiCl+0.80mol/l NaCl) of lithium chloride and sodium-chlor is mineralizer, and adding the sodium hydroxide solution adjust pH is 11, and control Chlorine in Solution ionic concn is 1mol/L.The compactedness that makes simultaneously autoclave is 90% (volume).After in the solution of autoclave top, placing the ZnO seed crystal of (0001) orientation, the seal pot mouth.Divide upper and lower two sections autoclave heated with nickel chromium triangle aluminium resistance wire; One group of resistance wire is warmed up to 300 ℃ at the bottom of the still; Above be warmed up to 240 ℃ near one group of resistance wire of seed crystal.Be incubated 40 days, get diameter and be 20 millimeters ZnO monocrystalline.
Claims (1)
1. the method for a developing zinc oxide body piece monocrystalline under hydrothermal condition, step is as follows:
As growth material, the high-temperature alloy steel that is placed on internal diameter Φ 8cm, high 0.5m is made autoclave base with 1 kilogram of closely knit briquetting of zinc oxide, and zinc oxide growth material top adds dividing plate, and the liner of autoclave is argent; Being filled with deionized water in autoclave, is mineralizer with the mixture 0.25mol/l LiCl+0.75mol/l NaCl of lithium chloride and sodium-chlor, and adding the sodium hydroxide solution adjust pH is 10, and control Chlorine in Solution ionic concn is 1mol/L; The compactedness that makes simultaneously autoclave is 90% volume; After in the solution of autoclave top, placing the ZnO seed crystal blocks of (0001) orientation, the seal pot mouth; Divide upper and lower two sections autoclave heated with nickel chromium triangle aluminium resistance wire; One group of resistance wire is warmed up to 280 ℃ at the bottom of the still; Above be warmed up to 230 ℃ near one group of resistance wire of seed crystal; Be incubated 38 days, get diameter and be 8 millimeters ZnO monocrystalline;
Perhaps,
As growth material, the high-temperature alloy steel that is placed on internal diameter Φ 10cm, high 2m is made autoclave base with 3 kilograms of closely knit briquettings of zinc oxide, and zinc oxide growth material top adds dividing plate, and the liner of autoclave is tetrafluoroethylene; Being filled with deionized water in reactor, is mineralizer with the mixture 0.25mol/l LiCl+0.80mol/l NaCl of lithium chloride and sodium-chlor, and adding the sodium hydroxide solution adjust pH is 11, and control Chlorine in Solution ionic concn is 1mol/L; The compactedness that makes simultaneously autoclave is 90% volume; After in the solution of autoclave top, placing the ZnO seed crystal of (0001) orientation, the seal pot mouth; Divide upper and lower two sections autoclave heated with nickel chromium triangle aluminium resistance wire; One group of resistance wire is warmed up to 300 ℃ at the bottom of the still; Above be warmed up to 240 ℃ near one group of resistance wire of seed crystal; Be incubated 40 days, get diameter and be 20 millimeters ZnO monocrystalline.
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| US6090202A (en) * | 1998-04-29 | 2000-07-18 | Sawyer Research Products, Inc. | Method and apparatus for growing crystals |
| WO2003029532A1 (en) * | 2001-10-01 | 2003-04-10 | Ceramare Corporation | Mineralizer composition and method for growing zinc oxide crystals, films and powders |
| CN1598076A (en) * | 2004-07-23 | 2005-03-23 | 清华大学 | Process for growing zine oxide monocrystal by hot water method |
| KR20070024884A (en) * | 2005-08-31 | 2007-03-08 | 한국화학연구원 | Method for the preparation of zinc oxide single crystal |
| CN101016648A (en) * | 2006-12-11 | 2007-08-15 | 中国科学院上海硅酸盐研究所 | Transition metal doping zinc oxide crystal and hydrothermal growth method for the same |
| CN101445267A (en) * | 2008-12-22 | 2009-06-03 | 重庆大学 | Method for Preparing black zinc oxide and application of black zinc oxide |
| JP2010053017A (en) * | 2008-04-04 | 2010-03-11 | Fukuda Crystal Laboratory | Zinc oxide single crystal and method for producing the same |
| CN101748485A (en) * | 2010-01-21 | 2010-06-23 | 桂林矿产地质研究院 | Preparation method for gallium-doped zinc oxide crystals |
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- 2011-03-18 CN CN 201110066466 patent/CN102127802B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1160017A (en) * | 1996-03-14 | 1997-09-24 | 中国科学技术大学 | Process for preparing nm phosphide and nitride by heat synthesis in organic solvent |
| US6090202A (en) * | 1998-04-29 | 2000-07-18 | Sawyer Research Products, Inc. | Method and apparatus for growing crystals |
| WO2003029532A1 (en) * | 2001-10-01 | 2003-04-10 | Ceramare Corporation | Mineralizer composition and method for growing zinc oxide crystals, films and powders |
| CN1598076A (en) * | 2004-07-23 | 2005-03-23 | 清华大学 | Process for growing zine oxide monocrystal by hot water method |
| KR20070024884A (en) * | 2005-08-31 | 2007-03-08 | 한국화학연구원 | Method for the preparation of zinc oxide single crystal |
| CN101016648A (en) * | 2006-12-11 | 2007-08-15 | 中国科学院上海硅酸盐研究所 | Transition metal doping zinc oxide crystal and hydrothermal growth method for the same |
| JP2010053017A (en) * | 2008-04-04 | 2010-03-11 | Fukuda Crystal Laboratory | Zinc oxide single crystal and method for producing the same |
| CN101445267A (en) * | 2008-12-22 | 2009-06-03 | 重庆大学 | Method for Preparing black zinc oxide and application of black zinc oxide |
| CN101748485A (en) * | 2010-01-21 | 2010-06-23 | 桂林矿产地质研究院 | Preparation method for gallium-doped zinc oxide crystals |
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