技术领域technical field
本发明属于光电材料技术领域，具体涉及一种纳米氧化锌光电功能材料的制备工艺，尤其涉及一种单分散、具有较低受激发射阈值和紫外发射能力增强的纳米氧化锌的溶胶凝胶低温制备工艺。The invention belongs to the technical field of optoelectronic materials, in particular to a preparation process of a nano-zinc oxide optoelectronic functional material, in particular to a sol-gel low-temperature monodisperse nano-zinc oxide with a lower stimulated emission threshold and enhanced ultraviolet emission capability Preparation Process.
背景技术Background technique
氧化锌光电信息功能材料的研究是1997年后刚刚兴起的，目前已成为非常热门的前沿课题。在1997年初日本和香港科学家首次报道了氧化锌薄膜室温下的近紫外受激光发射后，《Science》第276期立即以“Will UV Lasers Beat the Blues？”为题对此作了专门报道，称它是“一项伟大的工作”，因此，ZnO的紫外激光研究成为继GaN的蓝光热之后的又一热点。ZnO光电特性的研究之所以受到如此重视，是由于它有很多潜在的优点。首先，它是一种直接带宽禁带半导体，室温下的禁带宽度Eg＝3.36eV，与GaN(Eg＝3.4eV)相近，而它的激子结合能(60meV)却比GaN(21meV)高出许多，因此产生室温短波长发光的条件更加优越，而且ZnO可以在低于600℃温度下获得，不仅可以减少材料在高温制备时产生的杂质和缺陷，同时也大大简化了制备工艺；同时，ZnO来源丰富，价格低廉，又具有很高的热稳定性和化学稳定性。这些优点使ZnO成为一种潜在的、用途广泛的新一代短波长光电信息功能材料。在当今发展信息高速通信及高容量存储时代，紫外波段光电子器件，特别是该波段二极管激光器的实用化将具有重要的意义，因此，短波器件的商业应用前景极好。The research on zinc oxide optoelectronic information functional materials has just emerged after 1997, and has become a very popular frontier topic. In early 1997, Japanese and Hong Kong scientists reported the near-ultraviolet laser emission of zinc oxide film at room temperature for the first time, and the 276th issue of "Science" immediately made a special report on it under the title "Will UV Lasers Beat the Blues?", saying that It is "a great work", therefore, ZnO's ultraviolet laser research has become another hot spot after GaN's blue light heat. The research on the photoelectric properties of ZnO has received so much attention because it has many potential advantages. First of all, it is a direct bandgap semiconductor with a bandgap Eg=3.36eV at room temperature, which is similar to GaN (Eg=3.4eV), but its exciton binding energy (60meV) is higher than that of GaN (21meV). Therefore, the conditions for producing short-wavelength luminescence at room temperature are more favorable, and ZnO can be obtained at a temperature lower than 600 ° C, which can not only reduce the impurities and defects generated when the material is prepared at high temperature, but also greatly simplify the preparation process; at the same time, ZnO is rich in sources, low in price, and has high thermal and chemical stability. These advantages make ZnO a potential and versatile new-generation short-wavelength optoelectronic information functional material. In today's era of high-speed information communication and high-capacity storage, the practical application of ultraviolet-band optoelectronic devices, especially diode lasers in this band, will be of great significance. Therefore, the commercial application prospects of short-wave devices are excellent.
发明内容：Invention content:
本发明的目的在于提出一种全新的纳米氧化锌光电功能材料的溶胶凝胶制备工艺。The purpose of the present invention is to propose a new sol-gel preparation process of nano-zinc oxide photoelectric functional material.
本发明提出的纳米氧化锌光电功能材料的溶胶凝胶工艺，是以锌盐、络合剂、分散剂为原料，在水溶液中发生水解和缩合反应，以酸碱来控制反应体系的起始pH值，获得纳米氧化锌先体凝胶；经过真空干燥得氧化锌前驱体干凝胶；然后通过热处理，消除凝胶中的有机溶剂，得到氧化锌纳米粉体。具体步骤如下：The sol-gel process of nano-zinc oxide photoelectric functional material proposed by the present invention uses zinc salt, complexing agent and dispersant as raw materials, hydrolysis and condensation reactions occur in aqueous solution, and the initial pH of the reaction system is controlled by acid and alkali value, to obtain nano-zinc oxide precursor gel; vacuum drying to obtain zinc oxide precursor xerogel; and then heat treatment to eliminate the organic solvent in the gel to obtain zinc oxide nano-powder. Specific steps are as follows:
(1)将锌盐溶于去离子水中，搅拌均匀，配制成浓度为0.1～1mol/l的锌盐溶液；(1) dissolving the zinc salt in deionized water, stirring evenly, and preparing a zinc salt solution with a concentration of 0.1 to 1mol/l;
(2)在锌盐溶液中加入络合剂和分散剂，搅拌、混匀，锌盐和络合剂、分散剂用量的摩尔比为1∶1～3∶3～9；(2) Add complexing agent and dispersing agent in zinc salt solution, stir, mix, the mol ratio of zinc salt and complexing agent, dispersing agent consumption is 1: 1～3: 3～9;
(3)用酸碱度调节剂调节pH值呈弱酸性，一般pH值为3～7，在45～85℃水浴中搅拌4～8小时，获得氧化锌先体溶胶；(3) Use a pH regulator to adjust the pH value to be weakly acidic, generally the pH value is 3 to 7, and stir in a water bath at 45 to 85°C for 4 to 8 hours to obtain the zinc oxide precursor sol;
(4)继续搅拌直至溶胶成粘稠状，用无水乙醇洗涤后，经90～135℃真空干燥形成干凝胶；(4) Continue to stir until the sol becomes viscous, wash with absolute ethanol, and dry under vacuum at 90-135°C to form a xerogel;
(5)将干凝胶在空气中点燃或者在200～300℃进行预热处理(时间为1～3小时)，获得蓬松体产物，将其研磨，混匀；(5) Ignite the dry gel in the air or preheat it at 200-300°C (for 1-3 hours) to obtain a fluffy product, grind it, and mix it;
(6)再将该产物在450℃-650℃进行热处理，时间为1～3小时，即得纳米氧化锌粉体。(6) The product is then heat-treated at 450° C. to 650° C. for 1 to 3 hours to obtain nanometer zinc oxide powder.
本发明采用的锌盐可以为氯化锌、硫酸锌、乙酸锌或硝酸锌等。The zinc salt used in the present invention can be zinc chloride, zinc sulfate, zinc acetate or zinc nitrate and the like.
本发明采用的络合剂可以为甘氨酸、柠檬酸等。The complexing agent that the present invention adopts can be glycine, citric acid etc.
本发明采用的分散剂可以为乙二醇或其它亲液高分子等。The dispersant used in the present invention may be ethylene glycol or other lyophilic polymers.
本发明采用的酸碱度调节剂可以为碳酸氢氨、氢氧化钠或氨水氯化氨混合液等。The pH adjusting agent adopted in the present invention can be ammonium bicarbonate, sodium hydroxide or ammonia water ammonium chloride mixed solution and the like.
本发明在技术方案中，采用溶胶凝胶工艺，在低温下(小于600℃)制备出单分散纳米氧化锌量子点光电材料，即通过络合剂多齿配体和Zn配合，再加入分散剂，起类冠醚的作用，增强Zn与络合剂的组合。此外，分散剂的加入还能使胶粒变小、布朗运动激烈、扩散能力变强及动力学稳定性变大，即通过分散剂的作用，使整个溶液形成含长链有机分子的溶液，特别通过分散剂的聚合，待溶液蒸发浓缩成无水溶胶后，整个溶胶成为一个无规网络，使Zn在分子水平上按一定规律定位，使体系失去流动性，溶胶转变为凝胶。凝胶是胶体粒子相互联结成骨架而形成的空间网状结构，并在骨架结构中填满了液体，但网架间充满的液体不能流动，构成网架的胶体粒子具有一定的柔顺性，表现出弹性半固体状态。由于络合剂熔点比分散剂低，在加热干凝胶过程中，络合剂有机酸根离子首先开始分解，分散剂仍然固定着Zn在聚合物中的位置。整个热处理过程中，分散剂不断分解，样品内分解气体的压力迫使处于附近的Zn2+反应聚合，从而初步形成细小的颗粒，最终制得的纳米氧化锌具有量子点材料的光电子学特性，在室温下，成功实现了激子与激子、电子-空穴等离子体辐射复合受激发射，且有较低阈值和极高增益。从而解决了半导体材料紫外波段室温激光运转的困难，这对未来极端重要的短波长光电子器件的实际应用，特别是该波段二极管激光器的实用化将具有重要的意义。In the technical scheme of the present invention, a sol-gel process is adopted to prepare a monodisperse nano-zinc oxide quantum dot optoelectronic material at a low temperature (less than 600° C.), that is, the multi-dentate ligand of the complexing agent is coordinated with Zn, and then the dispersant is added. , which acts as a crown ether to enhance the combination of Zn and complexing agents. In addition, the addition of a dispersant can also make the colloidal particles smaller, the Brownian motion intense, the diffusion ability stronger and the dynamic stability larger, that is, through the action of the dispersant, the entire solution forms a solution containing long-chain organic molecules, especially Through the polymerization of the dispersant, after the solution is evaporated and concentrated into an anhydrous sol, the whole sol becomes a random network, so that Zn is positioned according to a certain rule at the molecular level, the system loses fluidity, and the sol turns into a gel. Gel is a spatial network structure formed by colloidal particles interconnected to form a skeleton, and the skeleton structure is filled with liquid, but the liquid filled between the grids cannot flow, and the colloidal particles that make up the grid have a certain degree of flexibility. out of the elastic semi-solid state. Since the melting point of the complexing agent is lower than that of the dispersant, the organic acid ions of the complexing agent first start to decompose during the heating and drying process, and the dispersant still fixes the position of Zn in the polymer. During the whole heat treatment process, the dispersant is continuously decomposed, and the pressure of the decomposed gas in the sample forces the nearby Zn2+ to react and polymerize, thereby initially forming fine particles. The final nano-zinc oxide has the optoelectronic properties of quantum dot materials. At room temperature, the recombination stimulated emission of exciton and exciton, electron-hole plasma radiation has been successfully realized, with a low threshold and extremely high gain. In this way, the difficulty of operating room temperature lasers in the ultraviolet band of semiconductor materials is solved, which will be of great significance to the practical application of extremely important short-wavelength optoelectronic devices in the future, especially the practical application of diode lasers in this band.
本发明采用溶胶-凝胶低温制备工艺，具有以下特点：合成的粉末硬团聚含量较少，可保持很高烧结活性，因而降低了反应温度；同时因采用无机盐和有机酸为先驱体和络合剂(分散剂)，易合成成分均匀的超细多组元粉末，成本低、易操作、可适于规模工业应用。另外，采用锌盐和一定比例的络合剂制备的无机聚合物干凝胶，具有自蔓延燃烧特性，燃烧过程是以锌盐的阴离子为氧化剂、络合剂为还原剂的氧化-还原反应，经自燃烧后可形成ZnO纳米粉体，通过调节凝胶中锌盐和络合剂的相对比例，可控制自燃烧过程，进而调控合成粉末的颗粒尺寸。The invention adopts sol-gel low-temperature preparation technology, which has the following characteristics: the synthesized powder has less hard agglomeration content and can maintain high sintering activity, thus reducing the reaction temperature; at the same time, because inorganic salt and organic acid are used as precursors and Mixture (dispersant), easy to synthesize ultra-fine multi-component powder with uniform composition, low cost, easy to operate, and suitable for large-scale industrial applications. In addition, the inorganic polymer xerogel prepared by using zinc salt and a certain proportion of complexing agent has self-propagating combustion characteristics. The combustion process is an oxidation-reduction reaction in which the anion of the zinc salt is used as the oxidant and the complexing agent is used as the reducing agent. ZnO nanopowder can be formed after self-combustion, and the self-combustion process can be controlled by adjusting the relative ratio of zinc salt and complexing agent in the gel, and then the particle size of the synthesized powder can be adjusted.
下面通过具体的实施例来进一步描述本发明的技术方案。The technical solutions of the present invention will be further described below through specific examples.
实施例1：Example 1:
1、将68克ZnCl2溶于1000ml的去离子水中搅拌10分钟，配制0.5mol/l的氯化锌溶液；1. Dissolve 68 grams of ZnCl2 in 1000ml of deionized water and stir for 10 minutes to prepare a 0.5mol/l zinc chloride solution;
2、200ml氯化锌溶液中，加入按1∶2∶6配置的甘氨酸和明胶，剧烈搅拌10分钟；2. Add glycine and gelatin in a ratio of 1:2:6 to 200ml of zinc chloride solution, and stir vigorously for 10 minutes;
3、用30～40ml碳酸氢氨调节溶液起始pH值为4，在85℃水浴中搅拌3小时，获得氧化锌先体溶胶；3. Use 30-40ml of ammonium bicarbonate to adjust the initial pH of the solution to 4, and stir in a water bath at 85°C for 3 hours to obtain the zinc oxide precursor sol;
4、继续搅拌1小时直至溶胶成粘稠状，用无水乙醇多次洗涤后，经90℃真空干燥形成干凝胶；4. Continue to stir for 1 hour until the sol becomes viscous, wash with absolute ethanol several times, and dry under vacuum at 90°C to form a xerogel;
5、将干凝胶在空气中点燃，获得蓬松体产物，将其研磨，混匀；5. Ignite the dry gel in the air to obtain a fluffy product, grind it and mix it;
6、将燃烧后产物在550℃进行热处理，获得比表面积为80m2/g，晶粒尺寸为20nm左右，具有单一纤锌矿结构的纳米氧化锌粉体，其在室温下产生近紫外波段发光，具有较低阈值和极高增益，有利于紫外波段光电子器件的实际应用。6. The combustion product is heat-treated at 550°C to obtain a nano-zinc oxide powder with a specific surface area of 80m2 /g, a grain size of about 20nm, and a single wurtzite structure, which emits light in the near-ultraviolet band at room temperature , with lower threshold and extremely high gain, which is beneficial to the practical application of optoelectronic devices in the ultraviolet band.
实施例2：Example 2:
1、将11.8克Zn(NO3)2·6H2O溶于200ml的去离子水中搅拌混匀，配制0.2mol/l的硝酸锌溶液；1. Dissolve 11.8 grams of Zn(NO3 )2 ·6H2 O in 200 ml of deionized water and stir to mix evenly to prepare a 0.2 mol/l zinc nitrate solution;
2、在上述硝酸锌溶液中，加入按1∶3配置的柠檬酸，剧烈搅拌10分钟；2. Add citric acid in a ratio of 1:3 to the above zinc nitrate solution, and stir vigorously for 10 minutes;
3、用20～30ml氨水调节溶液起始pH值为6.9左右，在50℃水浴中搅拌6小时，获得氧化锌先体溶胶；3. Use 20-30ml of ammonia water to adjust the initial pH of the solution to about 6.9, and stir in a water bath at 50°C for 6 hours to obtain the zinc oxide precursor sol;
4、继续搅拌2小时直至溶胶成粘稠状，用无水乙醇多次洗涤后，经120℃真空干燥形成干凝胶；4. Continue to stir for 2 hours until the sol becomes viscous, wash with absolute ethanol several times, and dry under vacuum at 120°C to form a xerogel;
5、将干凝胶在260℃进行预热处理，时间为1小时，获得蓬松体产物，将其研磨，混匀；5. Preheat the dry gel at 260°C for 1 hour to obtain a fluffy product, grind it, and mix it;
6、将上述产物在650℃进行热处理，获得比表面积为100m2/g，晶粒尺寸为10nm左右，具有单一纤锌矿结构的纳米氧化锌粉体，其在室温下产生近紫外波段发光，具有较低阈值和极高增益。6. The above product is heat-treated at 650°C to obtain a nano-zinc oxide powder with a specific surface area of 100m2 /g, a grain size of about 10nm, and a single wurtzite structure, which emits light in the near-ultraviolet band at room temperature. Has a low threshold and very high gain.
实施例3：Example 3:
1、9.15克乙酸锌溶于500ml的去离子水中搅拌10分钟，配制0.1mol/l的乙酸锌溶液；1. Dissolve 9.15 grams of zinc acetate in 500ml of deionized water and stir for 10 minutes to prepare a 0.1mol/l zinc acetate solution;
2、200ml乙酸锌溶液中，加入按1∶1.5∶3配置的甘氨酸和乙二醇，剧烈搅拌10分钟；2. Add glycine and ethylene glycol configured in a ratio of 1:1.5:3 to 200ml of zinc acetate solution, and stir vigorously for 10 minutes;
3、用5ml氨水和氯化氨的混合溶液调节溶液起始pH值为3，在75℃水浴中搅拌5小时，获得氧化锌先体溶胶；3. Adjust the initial pH value of the solution to 3 with a mixed solution of 5ml ammonia water and ammonium chloride, and stir in a water bath at 75°C for 5 hours to obtain the zinc oxide precursor sol;
4、继续搅拌1小时直至溶胶成粘稠状，用无水乙醇多次洗涤后，经135℃真空干燥形成干凝胶；4. Continue to stir for 1 hour until the sol becomes viscous, wash with absolute ethanol several times, and dry under vacuum at 135°C to form a xerogel;
5、将干凝胶在300℃进行预热处理，时间为1.5小时，获得蓬松体产物，将其研磨，混匀；5. Preheat the dry gel at 300°C for 1.5 hours to obtain a fluffy product, grind it, and mix it;
6、将上述产物在500℃进行热处理，获得比表面积为70m2/g，晶粒尺寸为25nm左右，具有单一纤锌矿结构的纳米氧化锌粉体，其在室温下产生近紫外波段发光。6. The above product is heat-treated at 500°C to obtain a nano-zinc oxide powder with a specific surface area of 70m2 /g, a grain size of about 25nm, and a single wurtzite structure, which emits light in the near-ultraviolet band at room temperature.
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| CN 200410054020CN1587061A (en) | 2004-08-26 | 2004-08-26 | Process for preparing sol-gel of nano zinc oxide by low temperature |
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| CN 200410054020CN1587061A (en) | 2004-08-26 | 2004-08-26 | Process for preparing sol-gel of nano zinc oxide by low temperature |
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| CN 200410054020PendingCN1587061A (en) | 2004-08-26 | 2004-08-26 | Process for preparing sol-gel of nano zinc oxide by low temperature |
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