CN114910522A - A kind of growth oxide hydrogen sensitive film based on MOCVD and preparation method thereof - Google Patents
A kind of growth oxide hydrogen sensitive film based on MOCVD and preparation method thereofDownload PDFInfo
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Abstract
Description
Translated fromChinese技术领域technical field
本发明属于半导体材料领域，具体为一种基于MOCVD生长氧化物氢敏薄膜及其制备方法。The invention belongs to the field of semiconductor materials, in particular to an oxide hydrogen sensitive film grown based on MOCVD and a preparation method thereof.
背景技术Background technique
氢气是一种能源载体，有助于解决化石燃料储备减少、能源供应安全和全球变暖的问题。与其他可燃气体和蒸气相比，如甲烷、丙烷或汽油蒸气等，氢气具有许多不寻常的特性。其中包括非常低的密度(0.0899kg/m3)和沸点(20.39K)以及高扩散系数(空气中0.61cm2/s)和浮力。就其燃烧特性而言，它的最小点火能量较低(0.017mJ)、燃烧热值高(142kJ/g)和宽可燃范围(4％～75％)以及高燃烧速度、爆炸灵敏度和点火温度为560℃。氢气也可以作为还原剂参与化学反应，对许多材料具有高渗透性，这使得其在某些应用中需要特殊的预防措施，氢能的安全使用和管理越来越受到重视，也是目前亟待解决的问题。Hydrogen is an energy carrier that helps address the problems of dwindling fossil fuel reserves, security of energy supply and global warming. Hydrogen has many unusual properties compared to other combustible gases and vapors, such as methane, propane or gasoline vapors. These include a very low density (0.0899 kg/m3 ) and boiling point (20.39 K) as well as a high diffusion coefficient (0.61 cm2 /s in air) and buoyancy. In terms of its combustion characteristics, it has a low minimum ignition energy (0.017mJ), a high combustion calorific value (142kJ/g), a wide flammable range (4% to 75%), and a high combustion rate, explosion sensitivity and ignition temperature of 560°C. Hydrogen can also participate in chemical reactions as a reducing agent and has high permeability to many materials, which makes it require special precautions in some applications. The safe use and management of hydrogen energy is receiving more and more attention, and it is also an urgent problem to be solved. question.
氢气传感器是一种检测氢气并产生与氢气浓度成正比的电信号的传感器装置。氢气传感器比传统的氢气检测方法(气相色谱仪、质谱仪)有几种优点，包括成本低、尺寸小、响应快。近几十年来，有许多不同类型的氢气传感器已经商业化或正在研发中。2015年，美国能源部(DOE)设定了极具挑战的氢气传感器使用性能参数指标，包括浓度范围(0.1％～10％)、工作温度(－30～80℃)、响应时间(＜1.0s)、气体环境(相对湿度10％～98％)、使用寿命(＞10年)、市场价格(每单元＜40美元)等。为了满足未来氢经济的需求，除了减少传感器大小、成本和功耗外，应提高氢气传感器灵敏度、选择性和稳定性。A hydrogen sensor is a sensor device that detects hydrogen and generates an electrical signal proportional to the hydrogen concentration. Hydrogen sensors have several advantages over traditional hydrogen detection methods (gas chromatographs, mass spectrometers), including low cost, small size, and fast response. In recent decades, many different types of hydrogen sensors have been commercialized or are under development. In 2015, the U.S. Department of Energy (DOE) set extremely challenging performance parameters for hydrogen sensors, including concentration range (0.1% to 10%), operating temperature (-30 to 80°C), response time (<1.0s ), gas environment (
半导体金属氧化物型氢气传感器包括具有半导体特性的金属氧化物层(通常是掺杂的氧化锡、氧化锌、氧化钨)，该金属氧化物层沉积在加热器上，从而将该层的温度升高至工作温度(500℃)。工作原理是环境中的氧气吸附在金属氧化物层时，该吸附层具有较高的电阻率，当氢气扩散到传感层并与氧反应后，吸附在半导体金属氧化物表面，吸附层的电阻率降低且下降值随氢气浓度的增加而增加。半导体金属氧化物型氢气传感器具有结构简单、价格便宜、灵敏度高、响应快、易于复合等优点，因此有利于大批量生产。The semiconducting metal oxide type hydrogen sensor includes a metal oxide layer (usually doped tin oxide, zinc oxide, tungsten oxide) with semiconducting properties, which is deposited on a heater, thereby increasing the temperature of the layer. Up to operating temperature (500°C). The working principle is that when oxygen in the environment is adsorbed on the metal oxide layer, the adsorption layer has a high resistivity. When the hydrogen diffuses into the sensing layer and reacts with oxygen, it is adsorbed on the surface of the semiconductor metal oxide, and the resistance of the adsorption layer is The rate decreases and the drop value increases with increasing hydrogen concentration. Semiconductor metal oxide hydrogen sensors have the advantages of simple structure, low price, high sensitivity, fast response, and easy recombination, so they are beneficial to mass production.
目前制备氧化物薄膜的方法主要包括金属有机物化学气相沉积(MOCVD)，磁控溅射法、真空蒸发沉积法，溶胶-凝胶法和喷雾热解法等。相对于其他薄膜材料的生长方式而言，用MOCVD生长可以得到结晶性能优良，实现大容量、大尺寸、均匀的氧化物薄膜生长，对其他元素的均匀掺杂控制更方便，可以生长出复杂组分的精细结构。同时，也有较广的成膜温度和薄膜沉积速率的生长范围，具有薄膜表面平滑、成膜均匀性好等特点。目前氧化锌还重要用于透明氧化物薄膜方面的研究，并没有对氢敏材料等有深入的研究。At present, the methods for preparing oxide thin films mainly include metal organic chemical vapor deposition (MOCVD), magnetron sputtering, vacuum evaporation deposition, sol-gel method and spray pyrolysis method. Compared with the growth methods of other thin film materials, MOCVD growth can obtain excellent crystalline properties, realize the growth of large-capacity, large-scale and uniform oxide thin films, and it is more convenient to control the uniform doping of other elements, and complex groups can be grown. The fine structure of the points. At the same time, it also has a wide growth range of film formation temperature and film deposition rate, and has the characteristics of smooth film surface and good film formation uniformity. At present, zinc oxide is also mainly used in the research of transparent oxide thin films, and there is no in-depth research on hydrogen sensitive materials.
综上所述，急需探索出一种高效的反应物组合以及开发一种适用于氢敏薄膜的氧化锌掺杂氧化铟和氧化锡基氧化物薄膜的MOCVD生长工艺。In conclusion, there is an urgent need to explore an efficient combination of reactants and develop a MOCVD growth process for ZnO-doped indium oxide and tin oxide-based oxide films suitable for hydrogen-sensitive films.
发明内容SUMMARY OF THE INVENTION
本发明的目的是针对现有技术中的不足，提供一种基于MOCVD生长氧化物氢敏薄膜及其制备方法。The purpose of the present invention is to provide a kind of growing oxide hydrogen sensitive film based on MOCVD and its preparation method aiming at the deficiencies in the prior art.
为实现上述目的，本发明采取的技术方案是：For realizing the above-mentioned purpose, the technical scheme that the present invention takes is:
一种基于MOCVD生长氧化物氢敏薄膜，其中：包括基底材料、氧化锌铟籽晶层和氧化物主体层；所述氧化锌籽晶层附着在基底材料的表面，所述氧化物主体层附着在氧化锌籽晶层的表面，氧化物主体层由锌、铟、锡通过MOCVD按比例生长获得。A kind of growing oxide hydrogen sensitive thin film based on MOCVD, which comprises a base material, a zinc indium oxide seed crystal layer and an oxide main body layer; the zinc oxide seed crystal layer is attached to the surface of the base material, and the oxide main body layer is attached On the surface of the zinc oxide seed layer, the oxide main layer is obtained by proportional growth of zinc, indium and tin by MOCVD.
在其中的一些实施例中，氧化锌籽晶层的厚度为20-50nm。In some of these embodiments, the thickness of the zinc oxide seed layer is 20-50 nm.
在其中的一些实施例中，氧化物主体层的厚度为50-200nm。In some of these embodiments, the oxide host layer has a thickness of 50-200 nm.
在其中的一些实施例中，氧化物主体层电阻率小于2×10-4Ω·cm。In some of these embodiments, the oxide bulk layer resistivity is less than 2×10−4 Ω·cm.
在其中的一些实施例中，氧化物主体层锌、锡与铟的原子数量比例为10000:1:100～10000:1:10。In some embodiments, the atomic ratio of zinc, tin and indium in the oxide host layer is 10000:1:100˜10000:1:10.
氧化物氢敏薄膜的制备方法，包括以下步骤：The preparation method of the oxide hydrogen sensitive film comprises the following steps:
步骤一、以硅片衬底作为基底材料，对基底材料表面进行有机和无机酸碱清洗后，放入MOCVD反应腔内，对硅片加热处理；Step 1, using the silicon wafer substrate as the base material, after cleaning the surface of the base material with organic and inorganic acids and bases, put it into the MOCVD reaction chamber, and heat the silicon wafer;
步骤二、以氩气作为保护气氛的情况下，向MOCVD反应腔内通入有机金属二乙基锌和氧气，使基底材料上生长出氧化锌籽晶层；Step 2, in the case of using argon gas as the protective atmosphere, introducing organic metal diethyl zinc and oxygen into the MOCVD reaction chamber, so that a zinc oxide seed crystal layer is grown on the base material;
步骤三、以氩气作为保护气氛的情况下，保持向MOCVD反应腔内通入有机金属二乙基锌和氧气，同时再向MOCVD反应腔通入有机金属三甲基铟，并掺入有机金属四(二甲氨基)锡，在籽晶层表面生长出氧化物主体层。Step 3: In the case of using argon as the protective atmosphere, keep feeding organometallic diethylzinc and oxygen into the MOCVD reaction chamber, and at the same time feed organometallic trimethylindium into the MOCVD reaction chamber, and add organometallic Tetrakis (dimethylamino) tin grows an oxide main layer on the surface of the seed layer.
步骤一前，具有MOCVD设备预处理步骤：运行MOCVD设备，调整温度为400℃进行预热，压力控制在50Torr，基座转速控制在350rpm，运行20分钟，进行MOCVD反应腔内清洁。Before step 1, there is a pretreatment step of MOCVD equipment: run the MOCVD equipment, adjust the temperature to 400°C for preheating, control the pressure at 50 Torr, control the rotation speed of the base at 350 rpm, run for 20 minutes, and clean the MOCVD reaction chamber.
步骤一中，基底材料放入MOCVD反应腔内后，控制温度在600℃，压力控制为10Torr，对硅片处理30min。In step 1, after the base material is put into the MOCVD reaction chamber, the temperature is controlled at 600° C., the pressure is controlled at 10 Torr, and the silicon wafer is processed for 30 minutes.
步骤二具体步骤为：调整MOCVD反应腔内温度在530℃，反应腔气压控制在9Torr，通入氩气作为保护气氛的情况下，通入有机金属二乙基锌和氧气，流量分别控制在1×10-5mol/min和6.5×10-2mol/min，生长出20-50nm的氧化锌籽晶层。The specific steps of step 2 are: adjusting the temperature in the MOCVD reaction chamber at 530° C., controlling the air pressure in the reaction chamber at 9 Torr, and introducing argon gas as a protective atmosphere, introducing organometallic diethyl zinc and oxygen, and the flow rate is controlled at 1 ×10-5 mol/min and 6.5×10-2 mol/min, 20-50nm zinc oxide seed layer was grown.
步骤三具体步骤为：调整MOCVD反应腔内在530℃，反应腔气压控制在25Torr，通入氩气作为保护气氛的情况下，保持向MOCVD反应腔内通入有机金属二乙基锌和氧气，再通入有机金属三甲基铟和氧气，流量分别控制在1×10-3mol/min和2.5×10-2mol/min，并掺入有机金属四(二甲氨基)锡，流量控制为与源瓶温度25℃，流量350sccm时获得的摩尔流量相同，在氧化锌籽晶层表面生长出50-200nm的氧化物主体层。The specific steps of step 3 are: adjusting the temperature in the MOCVD reaction chamber to 530°C, controlling the pressure of the reaction chamber at 25 Torr, and feeding argon gas as a protective atmosphere, keeping the organic metal diethylzinc and oxygen in the MOCVD reaction chamber, and then Organometallic trimethylindium and oxygen were introduced, and the flow rates were controlled at 1×10-3 mol/min and 2.5×10-2 mol/min, respectively, and organometallic tetrakis (dimethylamino) tin was added, and the flow rate was controlled to be the same as The same molar flow rate was obtained when the source bottle temperature was 25°C and the flow rate was 350 sccm, and an oxide main layer of 50-200 nm was grown on the surface of the zinc oxide seed layer.
本发明具有以下优点：The present invention has the following advantages:
1.本发明制备得到的氧化物外延膜的均匀性变异系数＜5％，对氢气的敏感程度<1S。1. The uniformity variation coefficient of the oxide epitaxial film prepared by the present invention is less than 5%, and the sensitivity to hydrogen is less than 1S.
2.本发明制备得到的氧化物氢敏薄膜还能精准控制生长质量和控制形貌，根据不同的应用需求可以形成粗糙度为1～50nm不同粗糙度的表面。2. The oxide hydrogen sensitive thin film prepared by the present invention can also precisely control the growth quality and control the morphology, and can form surfaces with different roughnesses ranging from 1 to 50 nm according to different application requirements.
3.采用MOCVD方法进行制备，便于量产，成品较低，在半导体氢敏薄膜领域具有良好的应用前景。3. The MOCVD method is used for preparation, which is convenient for mass production, and the finished product is low, and has a good application prospect in the field of semiconductor hydrogen sensitive films.
附图说明Description of drawings
图1是通断2％氢气1000次试验测试图；Figure 1 is a test chart of on-off 2%
图2是图1部分放大图。FIG. 2 is an enlarged view of a portion of FIG. 1 .
具体实施方式Detailed ways
下面将对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有作出创造性劳动的前提下所获得的所有其他实施例，都属于本发明保护的范围。The technical solutions in the embodiments of the present invention will be described clearly and completely below. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative work fall within the protection scope of the present invention.
需要说明的是，在不冲突的情况下，本发明中的实施例及实施例中的特征可以相互组合。It should be noted that the embodiments of the present invention and the features of the embodiments may be combined with each other under the condition of no conflict.
下面以具体实施例对本发明作进一步说明，但不作为本发明的限定。The present invention will be further described below with specific examples, but not as a limitation of the present invention.
一种基于MOCVD生长氧化物氢敏薄膜，其中：包括基底材料、氧化锌铟籽晶层和氧化物主体层；所述氧化锌籽晶层附着在基底材料的表面，所述氧化物主体层附着在氧化锌籽晶层的表面，氧化物主体层由锌、铟、锡通过MOCVD按比例生长获得。A kind of growing oxide hydrogen sensitive thin film based on MOCVD, which comprises a base material, a zinc indium oxide seed crystal layer and an oxide main body layer; the zinc oxide seed crystal layer is attached to the surface of the base material, and the oxide main body layer is attached On the surface of the zinc oxide seed layer, the oxide main layer is obtained by proportional growth of zinc, indium and tin by MOCVD.
氧化物氢敏薄膜指标如下：The indicators of the oxide hydrogen sensitive film are as follows:
氧化物氢敏薄膜在厚度方向上的电阻率小于2×10-4Ω·cm；The resistivity in the thickness direction of the oxide hydrogen sensitive film is less than 2×10-4 Ω·cm;
所述氧化物半导体氢敏薄膜厚度为70nm～250nm。The thickness of the oxide semiconductor hydrogen sensitive film is 70nm˜250nm.
所述氧化物半导体氢敏薄膜的主材为锌，掺杂源为铟和锡，锌、锡与铟的原子数量比例为10000:1:100～10000:1:10。The main material of the oxide semiconductor hydrogen sensitive film is zinc, the doping sources are indium and tin, and the atomic ratio of zinc, tin and indium is 10000:1:100-10000:1:10.
MOCVD是在气相外延生长(VPE)的基础上发展起来的一种新型气相外延生长技术。MOCVD is a new vapor phase epitaxy growth technology developed on the basis of vapor phase epitaxy (VPE).
MOCVD是以Ⅲ族、Ⅱ族元素的有机化合物和V、Ⅵ族元素的氧化物化物等作为晶体生长源材料，以热分解反应方式在衬底上进行气相外延，生长各种Ⅲ-V族、Ⅱ-Ⅵ族化合物半导体以及它们的多元固溶体的薄层单晶材料。MOCVD uses organic compounds of Group III and Group II elements and oxides of Group V and Group VI elements as crystal growth source materials, and conducts vapor phase epitaxy on the substrate by thermal decomposition reaction to grow various III-V Groups, Thin-layer single-crystal materials of II-VI compound semiconductors and their multicomponent solid solutions.
氧化物氢敏薄膜的制备方法如下：The preparation method of the oxide hydrogen sensitive film is as follows:
1，MOCVD设备预处理：运行MOCVD设备，调整温度为400度进行预热，压力控制在50Torr，基座转速控制在350rpm，运行20分钟，进行腔体内清洁。1. Pretreatment of MOCVD equipment: run the MOCVD equipment, adjust the temperature to 400 degrees for preheating, control the pressure at 50 Torr, control the base speed at 350 rpm, run for 20 minutes, and clean the cavity.
2，基底预处理：以硅片(蓝宝石)衬底作为基底材料，对基底材料表面进行有机和无机酸碱清洗后，放入MOCVD反应腔内，控制温度在600℃，压力控制为10Torr，处理30min。2. Substrate pretreatment: using silicon wafer (sapphire) substrate as the substrate material, after organic and inorganic acid-base cleaning on the surface of the substrate material, it is placed in the MOCVD reaction chamber, the temperature is controlled at 600 °C, and the pressure is controlled at 10 Torr. 30min.
3，氧化锌缓冲晶层生长：调整生长温度保持在530℃，反应腔气压控制在9Torr，通入氩气作为保护气氛的情况下，通入有机金属二乙基锌和氧气，流量分别控制在1×10-5mol/min和6.5×10-2mol/min，生长出20nm的缓冲层.3. Growth of zinc oxide buffer crystal layer: adjust the growth temperature to keep at 530 °C, control the pressure of the reaction chamber at 9 Torr, and pass in argon as a protective atmosphere, pass in organometallic diethylzinc and oxygen, and control the flow rate at1 ×10-5 mol/min and 6.5×10-2 mol/min, a 20nm buffer layer was grown.
4，氧化物主体层生长：调整生长温度保持在530℃，反应腔气压控制在25Torr，通入氩气作为保护气氛的情况下。在通入有机金属三甲基铟和氧气，流量分别控制在1×10-3mol/min和2.5×10-2mol/min，并掺入有机金属四(二甲氨基)锡，流量控制为与源瓶温度25℃，在籽晶层表面生长出70nm的主体层。4. Growth of the oxide body layer: adjust the growth temperature to keep at 530°C, control the pressure of the reaction chamber at 25 Torr, and pass argon gas as a protective atmosphere. After passing in organometallic trimethylindium and oxygen, the flow rates were controlled at 1×10 -3mol /min and 2.5×10-2 mol/min, respectively, and organometallic tetrakis(dimethylamino)tin was added, and the flow rate was controlled as At the source bottle temperature of 25°C, a bulk layer of 70 nm was grown on the surface of the seed layer.
本实施例中的氧化物氢敏薄膜经过HallHL5500测试仪测试，测得电阻率低于2×10-4Ω·cm。The oxide hydrogen sensitive film in this example was tested by HallHL5500 tester, and the measured resistivity was lower than 2×10-4 Ω·cm.
本实施例氧化物透明导电薄膜的表面形貌，本实施例制得的薄膜晶粒大小在50-100nm，且薄膜具有较粗糙表面形貌。The surface morphology of the oxide transparent conductive film in this example shows that the grain size of the film prepared in this example is 50-100 nm, and the film has a relatively rough surface morphology.
如图1-2所示，本实施例中制得的氢敏薄膜在测试中，对氢气的敏感程度<1S。As shown in Figure 1-2, the hydrogen-sensitive film prepared in this example has a sensitivity to hydrogen <1S in the test.
以上仅是本发明的优选实施方式，本发明的保护范围并不仅局限于上述实施例，凡属于本发明思路下的技术方案均属于本发明的保护范围。应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理前提下的若干改进和润饰，应视为本发明的保护范围。The above are only preferred embodiments of the present invention, and the protection scope of the present invention is not limited to the above-mentioned embodiments, and all technical solutions that belong to the idea of the present invention belong to the protection scope of the present invention. It should be pointed out that for those skilled in the art, some improvements and modifications without departing from the principle of the present invention should be regarded as the protection scope of the present invention.
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