多孔电极平板结构的PdPc/H_2PtCl_6杂化有机半导体毒气传感器的研究

Study on PdPc/H_2PtCl_6 hybridized organic semiconductor poison gas sensor of porous electrode flat structure

采用“摸扳法”以对甲基苯酚、4-硝基邻苯二晴为原材料，以N，N二甲基甲酰胺为溶剂，在N2保护和碳酸钾的催化作用下，合成了酞菁分子碎片，通过质谱分析确定了相对分子质量为243（理论值为243．34），验证了工艺过程的正确性。以共溶技术将分子碎片与氯化钯在正戊醇、DBU作用下合成墨绿色四取代对甲苯氧基PdPc，通过红外吸收光谱分析验证了其吸收峰的测量值与理论值基本吻合，确定了合成反应终产物，进而以一定比例将PdPc、HzPtCle共溶在甲醇溶液中，在30～50℃下48h杂化合成为有机半导体气敏材料。依据欧姆定律，并以激光微加工、半导体技术设计、制诈了多孔电极平板结构，增大电极面积，降低了电极间距，比常用叉指电极结构的电阻降低了10。倍以上，使其电导率接近无机半导体数量级，利于后续电路信号采集。通过电镜观察了多孔电极的微观SEM形貌，确定其为连续、多孔的表面态，气孔在Ф0．1～Ф2μm，既保证了导电，又有透气的特征。以真空镀膜技术将气敏材料形成气敏膜，电镜观察其气敏膜的微观SEM形貌，基本层膜厚2μm，并有Ф0．1～Ф5μm微球结晶体嵌入，分布匀一，呈现继续互融生长趋势。以静态法测量其气敏特性，结果表明传感器对NO2呈N型半导体，0．010％气体浓度下灵敏度为7．45倍；对NO呈P型半导体，0．010％气体浓度下灵敏度为0．25倍；响应时间为90s。对气体不同的变化规律说明其的气敏机理与气体性能有关。

Phthalocyanine molecular fragments were synthesized in template-based method using methyphenol, 4-nitro phthalonitrile as raw materials and N, N dimethyl formamide as solvent under the catalysis of potassium in nitrogen atmosphere. Its molecular weight was confirmed to be 243 （theoretical value is 243.34） through mass spectrography. Then through the altogether-dissolve, under the action of pentanol and DBU, molecular fragments and palladium bichloride were synthesized to form the atrovirens 4-methoxy benzoic PdPc. The measured value of absorption peak by infrared absorption spectroscopy was fundamentally uniform to the theoretical value, so that the synthetic reaction end product was determined. Further, PdPc and H2PtCl6 was dissolved in carbinol in a given proportion to synthesize for 48 h to form organic semiconductor sensitive material. According to Ohm＇s law and using laser micro-machining and semiconductor techniques, a porous electrode flat structure was fabricated in the electrodes＇ area increased while the space reduced, its resistance reduces more than 10a times than interdigital electrode in common use, in approach to abio-semiconductor＇s conductivity. Experimental results show it is good for subsequent circuit signal＇s collection. Through electron scan, its mirco-appearance was observed to be continuous and porous. The air hole was Ф0.1-Ф2μm, this not only ensure its conduction but also has ventilate characteristic. Through vacuum deposition, the sensitive material was made to be a sensitive film. Under electron scan, the film＇s fundamental thickness was 2μm and has Ф0. 1- Ф5 μm micro-ball crystal embed, uniform distributed, appeared continual mutual fuse growth. Using a static state method to measure its sensitive characteristic, the measurement indicates that the sensor appears N type semiconductor to NO2, the sensitivity is 7.45 times when the gas density is 0. 010% ; the sensor appears P type semiconductor to NO, the sensitivity is 0. 25 times when the gas density is 0.010% ; the response time is 90s. The change rule to different gases indicates its gas sensitive principle is related to the gas capability.