CN1317427C - Process for growing zine oxide monocrystal by hot water method - Google Patents
Process for growing zine oxide monocrystal by hot water method Download PDFInfo
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- CN1317427C CN1317427C CNB2004100093676A CN200410009367A CN1317427C CN 1317427 C CN1317427 C CN 1317427C CN B2004100093676 A CNB2004100093676 A CN B2004100093676A CN 200410009367 A CN200410009367 A CN 200410009367A CN 1317427 C CN1317427 C CN 1317427C
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- zinc oxide
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Abstract
The present invention relates to a method for growing zinc oxide monocrystal by a water heating method, which belongs to the field of inorganic non-metal material. The present invention has the main content that zinc hydroxide is used as a predecessor, ammonia water is used as a mineralizing agent, and the zinc hydroxide and the ammonia water are heated in a high pressure axe to grow the zinc oxide crystals; a heating way can be a microwave heating way or a resistance wire heating way, the grown crystals can be zinc oxide nanometer fiber or the zinc oxide monocrystal. The present invention has the advantages of simple manufacturing process and low cost; furthermore, the present invention can control the size of the zinc oxide crystals by changing technological conditions.
Description
Technical field
The present invention relates to a kind of method, belong to field of inorganic nonmetallic material with the Hydrothermal Preparation zincite crystal.
Background technology
Characteristics such as zinc oxide has that energy gap is big, electronic migration saturation rate height, specific inductivity are little, Heat stability is good are to make blue, green luminescence device, the third generation semiconductor material of radioprotective, high frequency, high-power and high-density integrated-optic device; At photoelectric field, zinc oxide can also be applied to collection optics such as solar cell, color sensor; Because the mechanics of Zinc oxide single crystal body fiber and the performance that physical and chemical performance approaches desirable single crystal are so zinc oxide fiber can be widely used as the strongthener of pottery, rubber, resin, plastic or other material; In addition zinc oxide fiber the conduction of matrix material, antistatic, inhale ripple, sound absorption, vibration damping, also there is extensive use in wear-resisting field such as anti-skidding.In a word, no matter be fibrous zinc oxide or block zinc oxide material, in national economy and national defense construction, all there is important use to be worth.
The zinc oxide large single crystal is synthetic mainly to be to adopt following three kinds of methods: flux method, chemical vapour transport method and hydrothermal method.In these three kinds of methods, characteristics such as hydrothermal method synthetic crystal has the purity height, defective is few, thermal stresses is little, quality is good, and also the crystal growth rate of this synthetic method is also bigger.People (Eriko Ohshima such as Japan Eriko Ohshima, Hiraku Ogino, Ikuo Niikura, et al.Journal of Crystal Growth, 2004,260,166～170) be that mineralizer, agglomerating ZnO polycrystalline are precursor with LiOH (1mol/l) and KOH (3mol/l), hydro-thermal synthesizes large single crystal ZnO.Because the alkalescence in the hydrothermal solution is stronger, will add the Pt liner that can seal in autoclave; The ZnO crystal that synthesizes contains impurity such as Li, K, Al and Fe.This shows that because mineralizer alkalescence is strong, make synthesis technique complexity, cost height, the impurity that contains is also higher.
The method for preparing the Zinc oxide single crystal fiber has a lot, and known have: the one, earlier pure zinc silk arc is melted and sprayed powder, and zinc powder carries out after the special processing dry again in the aqueous solution, allows the zinc powder surface form the compactness oxide film, and zinc oxide content reaches 18% in the zinc powder.Surface film oxide can suppress metallic zinc and flow out fast from granule interior, is also controlling the rate of migration of oxygen to zinc granule inside, needed time of bonding crystal growth simultaneously.The 2nd, be mixing raw material with zinc powder and coke powder, be laid on container bottom, be heated to certain temperature in the atmosphere, metallic zinc steam is at CO
2, CO, O
2Be under certain oxygen gesture in the mixed atmosphere, slow oxidation, deposition growing, thus form Zinc oxide single crystal body fiber.The 3rd, ZnO powder and activated carbon powder are placed in the porcelain boat by the suitable proportion mixing.N
2And O
2Mixed gas feed reaction chamber by a certain percentage, temperature is controlled at 1050～1150 ℃, reacts can make Zinc oxide single crystal body macrofiber in 5 hours.The main drawback of these methods is the requirement height to raw material, the process control strictness, and some technology is complicated, so the production cost height.Also have Chinese patent CN 1305024A to disclose and a kind ofly directly prepare the long stapled method of single crystal from zinc sulphide.This method is to contain the zinc sulphide of zinc 20～70% and carbonaceous reducing agent, lime, calcined dolomite, yellow soda ash pack into container, heating in air atmosphere, reaction behind batching, mixing, finally to obtain Zinc oxide single crystal body macrofiber.This kind method also needs through pyroprocess, and energy consumption is high and easily cause and produce higher reunion between particle and sneak into shortcoming such as impurity easily.
Summary of the invention
The purpose of this invention is to provide a kind of method of obtaining the Zinc oxide single crystal body macrofiber that crystal development is complete, purity is high or growing zinc oxide block monocrystalline.
The zinc hydroxide that to the effect that utilizes of the present invention is as precursor, put it in the deionized water, make mineralizer with ammoniacal liquor, pH value in the hydrothermal solution is modulated to＞11, add in the reaction autoclave then, be heated to 100 ℃～400 ℃ of differing tempss in autoclave, constant temperature time is 1 hour～40 days, carries out the growth of Zinc oxide single crystal body.
Concrete preparation method is as follows:
The precursor zinc hydroxide is added deionized water forms solution and making beating, add ammoniacal liquor make pH value in the solution be modulated to＞11, then slurries are added in the reaction autoclave; Be heated to 100 ℃～200 ℃, constant temperature naturally cooled to room temperature after 2～5 hours, filtered to isolate precipitation; Obtain Zinc oxide single crystal body macrofiber after will precipitating drying.
Zinc hydroxide is pressed into high-temperature alloy steel that closely knit fragment (2～3 centimetres of sizes) is placed on internal diameter Φ 30cm, high 3m makes autoclave base (on add dividing plate), use ammoniacal liquor NH
3H
2O makes mineralizer, the pH value in the hydrothermal solution is modulated to＞11, charging in the autoclave, compactedness is 85%.After in the solution of autoclave top, placing the ZnO seed crystal several piece of (001) orientation, the seal pot mouth.Divide three sections of upper, middle and lower to autoclave heating (260 ℃～300 ℃) with nickel-chromium resistance wire or nickel chromium triangle aluminium high-temperature electric heat silk, be incubated 30～40 days, on seed crystal, can grow large-sized ZnO monocrystalline.
Zinc oxide crystallization solvent for use is a deionized water.
The invention has the advantages that: under weak basic condition, synthesize highly purified Zinc oxide single crystal body macrofiber or block Zinc oxide single crystal through hydro-thermal reaction.Technology is simple, cost is low, can come controlled oxidation zinc crystalline size by change reaction times, temperature.To satisfy different requirements to zincite crystal.
Embodiment
Embodiment 1:
Precursor zinc hydroxide powder is added deionized water, form solution and making beating, add ammoniacal liquor the pH value in the solution is modulated to greater than 11, then slurries are added in the autoclave; Make solution quickly heat up to 100 ℃ with 50 ℃/minute heat-up rate with microwave heating, constant temperature naturally cooled to room temperature after 2 hours, filtered to isolate precipitation, obtained Zinc oxide single crystal body hexa-prism macrofiber after will precipitating drying.Its average length is that 4 μ m, mean diameter are 200nm.Scanning electron microscopic observation shows that fiber is the line crystals growth, and fiber is all consistent substantially with fiber thickness, but the diameter of every fiber is almost constant.Product is through X-ray diffraction analysis, and the result is indicated as the Zinc oxide single crystal body macrofiber of based on very high purity.
Embodiment 2:
Precursor zinc hydroxide powder is added deionized water, form solution and making beating, add ammoniacal liquor the pH value in the solution is modulated to greater than 11, then slurries are added in the autoclave; Make solution quickly heat up to 200 ℃ with 40 ℃/minute heat-up rate with microwave heating, constant temperature naturally cooled to room temperature after 2 hours, filtered to isolate precipitation, obtained Zinc oxide single crystal body hexa-prism macrofiber after will precipitating drying.Its average length is that 10 μ m, mean diameter are 500nm.
Embodiment 3:
Precursor zinc hydroxide powder is added deionized water, form solution and making beating, add ammoniacal liquor the pH value in the solution is modulated to greater than 11, then slurries are added in the autoclave; Make solution quickly heat up to 100 ℃ with 50 ℃/minute heat-up rate with microwave heating, constant temperature naturally cooled to room temperature after 5 hours, filtered to isolate precipitation, obtained Zinc oxide single crystal body hexa-prism macrofiber after will precipitating drying.Its average length is that 6 μ m, mean diameter are 300nm.
Embodiment 4:
As substratum, the high-temperature alloy steel that is placed on internal diameter Φ 30cm, high 3m is made autoclave base (on add dividing plate), uses ammoniacal liquor NH with three kilograms of closely knit fragments of zinc hydroxide (2～3 centimetres of sizes)
3H
2O makes mineralizer, the pH value in the hydrothermal solution is modulated to 〉=12, charging in the autoclave, compactedness is 85%.After in the solution of autoclave top, placing the ZnO seed crystal several piece of (001) orientation, the seal pot mouth.With three sections of nickel-chromium resistance wire or nickel chromium triangle aluminium high-temperature electric heat silk branch upper, middle and lower autoclave is heated: one group of heater strip is warmed up to 300 ℃ at the bottom of the still; Middle one group is warmed up to 280 ℃; Above one group be warmed up to 260 ℃ for one group near seed crystal.Be incubated 40 days, on seed crystal, can grow the ZnO monocrystalline of hundreds of grams.
Claims (3)
1. 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, add then 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.
2. the method for Hydrothermal Growth Zinc oxide single crystal according to claim 1 is characterized in that described precursor zinc hydroxide is closely knit block.
3. the method for Hydrothermal Growth Zinc oxide single crystal according to claim 1 is characterized in that described precursor zinc hydroxide is a powder.
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| CNB2004100093676A CN1317427C (en) | 2004-07-23 | 2004-07-23 | Process for growing zine oxide monocrystal by hot water method |
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| CN1317427C true CN1317427C (en) | 2007-05-23 |
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Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1308244C (en) * | 2005-04-26 | 2007-04-04 | 华中师范大学 | Nano zine oxide with excitating light strength and frequency tuning fluorescent frequency and it preparation |
| CN1298894C (en) * | 2005-06-08 | 2007-02-07 | 中国科学院上海光学精密机械研究所 | Method for improving growth efficiency and quality of ZnO crystal grown by hydrothermal method |
| CN100451180C (en) * | 2005-11-30 | 2009-01-14 | 中国科学院半导体研究所 | Method for growing ZnO mono-crystalline by closed pipe chemical vapour transmission |
| CN100580155C (en) * | 2006-12-11 | 2010-01-13 | 中国科学院上海硅酸盐研究所 | Method for developing zinc oxide crystallite by chemical gas-phase transmitting process |
| CN101319371B (en) * | 2008-05-14 | 2010-12-15 | 陕西科技大学 | Production method of spindle-shaped nano ZnO monocrystal |
| CN102127802B (en) * | 2011-03-18 | 2013-01-02 | 山东大学 | Method for growing zinc oxide monocrystalline under hydrothermal condition by utilizing mineralizer |
| CN102337581B (en) * | 2011-09-20 | 2014-05-07 | 清华大学 | Method for preparing zinc oxide crystal whisker by using recyclable solvent in low-temperature hydrothermal way |
| CN111220654A (en) * | 2019-12-04 | 2020-06-02 | 清华大学 | Zinc oxide crystal boundary aging migration ion identification method |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0587407A2 (en) * | 1992-09-08 | 1994-03-16 | Ngk Insulators, Ltd. | Piezoelectric semiconductor and process for production thereof |
| JPH06279192A (en) * | 1993-03-29 | 1994-10-04 | Ngk Insulators Ltd | Piezoelectric semiconductor and its production |
| JPH07242496A (en) * | 1994-03-03 | 1995-09-19 | Ngk Insulators Ltd | Method for growing zinc oxide single crystal |
-
2004
- 2004-07-23 CN CNB2004100093676A patent/CN1317427C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0587407A2 (en) * | 1992-09-08 | 1994-03-16 | Ngk Insulators, Ltd. | Piezoelectric semiconductor and process for production thereof |
| US5393444A (en) * | 1992-09-08 | 1995-02-28 | Ngk Insulators, Ltd. | Piezoelectric semiconductor |
| JPH06279192A (en) * | 1993-03-29 | 1994-10-04 | Ngk Insulators Ltd | Piezoelectric semiconductor and its production |
| JPH07242496A (en) * | 1994-03-03 | 1995-09-19 | Ngk Insulators Ltd | Method for growing zinc oxide single crystal |
Non-Patent Citations (3)
| Title |
|---|
| 氧化锌晶体的研究进展 宋词，杭寅，徐军，人工晶体学报，第33卷第1期 2004 * |
| 水热法合成氧化锌晶体 董国义 韦志仁等，人工晶体学报，第32卷第2期 2003 * |
| 水热法合成氧化锌晶体 董国义 韦志仁等，人工晶体学报，第32卷第2期 2003;氧化锌晶体的研究进展 宋词，杭寅，徐军，人工晶体学报，第33卷第1期 2004 * |
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