【作者】 夏道成；

【导师】 杜国同；

【作者基本信息】 大连理工大学 ， 微电子学与固体电子学， 2008， 博士

【摘要】 本论文主要是对新型取代基酞菁和酞菁晶体的合成和光学性质进行了研究。因为酞菁在信息、医疗、化工等众多领域有很广泛的应用，所以近百年来一直是科学家研究的热点课题。酞菁经过近百年的研究，科学家已经合成了上万种酞菁衍生物，但是，随着科技的不断进步，人类社会不断发展的需求，具有新特性的新型酞菁的获得仍是相关科技工作者孜孜以求的目标。为此，在本论文中，我们改进了合成方法，合成了几种新型酞菁，还制备了其电致发光器件。我们首次合成了九个新型不对称酞菁。它们分别是2（3）-（对叔丁基苯氧基）酞菁、2（3）-（对叔丁基苯氧基）酞菁铜、2（3）-（对叔丁基苯氧基）酞菁锌、2（3），16（17）-二-（对叔丁基苯氧基）酞菁、2（3），16（17）-二-（对叔丁基苯氧基）酞菁铜、2（3），16（17）-二-（对叔丁基苯氧基）酞菁锌、2（3），9（10），16（17）-三-（对叔丁基苯氧基）酞菁、2（3），9（10），16（17）-三-（对叔丁基苯氧基）酞菁铜和2（3），9（10），16（17）-三-（对叔丁基苯氧基）酞菁锌。不对称酞菁是以4-（对叔丁基苯氧基）邻苯二腈（A）、1，3-二亚胺基异吲哚啉（B）和金属盐（二水乙酸合铜和二水乙酸合镍）为起始原料合成的。合成方法简述如下：原料在不同的有机溶剂（正戊醇，喹啉，N，N-二甲基甲酰胺）中加热搅拌，加入适量的催化剂1，8-二氮杂-双环（5，4，0）十一碳烯-7（DBU），在氮气保护下进行反应。反应完毕后，在减压下除去溶剂，首先产物用甲醇在索氏提取器中索提24 h，然后产物用柱层析分离两次后，最后得到目标化合物。不对称酞菁经过元素分析、红外、紫外可见光谱和质谱的表征证明其结构，从而证实产物就是目标化合物。我们首次用喹啉为溶剂的溶剂热合成法直接合成了酞菁铜晶体。我们使用三种原料合成酞菁铜晶体：一是邻苯二腈、钼酸铵和二水乙酸合铜为起始原料；二是1，3-二亚胺基异吲哚啉和二水乙酸合铜为起始原料；三是邻苯二腈、氧化铜和钼酸铵为起始原料。在实验中我们得到了2 mm～10．5 mm长的酞菁铜晶体，适合四元衍射测量。通过四元衍射和XRD的测量证明，晶体是四环非氮杂酞菁铜。酞菁铜分子式是CuN₈C₃₂H₁₆，单晶空间群是P 2（1）／n，参量是：a=14．668（3），b=4．8109（10），c=19．515（7），α=90，β=121．04（2），γ=90，单元体积是1179．91（?）³，根据XRD图与标准的图卡，比较峰的强度与位置，证实该晶体是β型晶体。在实验中得到的最长针状酞菁铜单晶尺寸是10．5 mm。我们还讨论了酞菁铜晶体产率与反应温度、反应时间和反应时所用溶剂体积的关系（原料质量固定时）。以1，3-二亚胺基异吲哚啉和二水乙酸合铜为起始原料时，发现合成酞菁铜晶体的产率最高，为52．3％；最佳的反应条件是：反应温度为270℃，反应溶剂为10 ml，反应时间为8 h。本文还首次以喹啉为溶剂的溶剂热合成法直接合成了酞菁镍晶体。我们使用两种原料合成酞菁镍晶体：一是邻苯二腈和二水乙酸合镍为起始原料：二是1，3-二亚胺基异吲哚啉、钼酸铵和二水乙酸合镍为起始原料。在合成中得到酞菁镍晶体尺寸也在2 mm～10．5 mm，适合四元衍射测量。通过四元衍射和XRD的测试证明，晶体是四环非氮杂酞菁镍。酞菁镍分子式是CuN₈C₃₂H₁₆，单晶空间群是P 2（1）／n，参量是：a=14．784（3），b=4．7104（9），c=17．398（4），β=90，β=104．38（2），γ=90，单元体积是1173．6 （?）³，根据XRD图与标准的图卡，比较峰的强度与位置，证实该晶体也是β型晶体。然后我们研究了酞菁镍晶体产率与反应温度、反应时间和反应时所用溶剂体积的关系。我们又研究发现，以1，3-二亚胺基异吲哚啉、钼酸铵和二水乙酸合镍为起始原料合成酞菁镍晶体时的产率最高，为56．84％,最佳的反应条件是：在270℃下，溶剂为14 ml，时间是8 h。用上述方法合成酞菁，其优点是可以直接合成酞菁铜（镍）晶体，十分方便。我们相信，在不久的将来，该方法可以推广到酞菁铜晶体的工业化生产中。我们以三种新型不对称酞菁铜为发光层制作了电致发光器件。三种新型不对称酞菁铜为：一是2（3）-（对叔丁基苯氧基）酞菁铜；二是2（3），9（10），16（17）-三-（对叔丁基苯氧基）酞菁铜；三是以2（3），16（17）-二-（对叔丁基苯氧基）酞菁铜。一种是以2（3）-（对叔丁基苯氧基）酞菁铜和2（3），9（10），16（17）-三-（对叔丁基苯氧基）酞菁铜为发光层的器件结构为：ITO／NPB（40 nm）／Pc（30 nm）／AlQ（43．8 nm）／LiF（0．5nm）／Al（120 nm）。ITO为阳极；NPB为空穴传输层；Pc为发光层；Alq₃为电子传输层；LiF为修饰电极：Al为阴极。器件的制备工艺大体为：在5．0～9．0×10^-4Pa，采用热蒸镀的方法，把各个有机材料依次蒸镀到清洗过的ITO玻璃衬底上，其中NPB生长速度为20 （?）／min；Pc[2（3）-（对叔丁基苯氧基）酞菁铜]生长速度为3（?）／min，Pc[2（3），9（10），16（17）-三-（对叔丁基苯氧基）酞菁铜]生长速度为1（?）／min；AlQ生长速度为20（?）／min；最后，蒸镀LiF和Al，制作OLED。ITO在测试波段的透过率大于80％。另一种是以2（3），16（17）-二-（对叔丁基苯氧基）酞菁铜为发光层的器件结构为：ITO／NPB（30 nm）／Pc（30 nm）／BCP（20 nm）／AlQ（30 nm）／LiF（0．5 nm）／Al（120 nm）。ITO为阳极；NPB为空穴传输层；Pc为发光层：BCP为空穴阻挡层：Alq₃为电子传输层：LiF为修饰电极；Al为阴极。器件的制备工艺大体为：在5．0～9．0×10^-4Pa，采用热蒸镀的方法，把有机材料依次蒸镀到清洗过的ITO玻璃衬底上，其中NPB生长速度为20 （?）／min；Pc[2（3），16（17）-二-（对叔丁基苯氧基）酞菁铜]生长速度为2 （?）/min；BCP生长速度为15（?）／min；AIQ生长速度为20（?）/min；最后，蒸镀LiF和Al，制作OLED。器件特性：以2（3）-（对叔丁基苯氧基）酞菁铜为发光层与Q带相关联的发射波长分别出现在869 nm和1062 nm；以2（3），16（17）-二-（对叔丁基苯氧基）酞菁铜为发光层与Q带相关联的发射波长分别出现在1050nm和1110 nm；以2（3），9（10），16（17）-三-（对叔丁基苯氧基）酞菁铜为发光层与Q带相关联的发射波长分别出现在1095 nm和1204nm。上述发射波长的不同是因为取代基的数目和真空镀膜的分子聚集态不同造成的，所以三种不对称酞菁铜的发射峰值和半峰宽差别较大，而且由此也引起斯托克司位移的不同。我们首次合成了亚酞菁铜。合成方法简述如下：把1，3-二亚胺基异吲哚啉、钼酸铵和二水乙酸合铜在喹啉里加热，加入催化剂量的DBU进行反应。反应完毕后，通过索氏提取，然后用柱层分析分离，得到灰褐色产物。通过质谱分析和元素分析数据证实，灰褐色产物就是目标化合物亚酞菁铜。根据亚酞菁铜分子裂解质谱图，我们还初次分析了亚酞菁铜分子的裂解过程，首次给出亚酞菁铜合成的反应机理。更多还原

【Abstract】 In this dissertation, we study the synthesis and optical character of new substituted Phthalocyanines （Pcs） and phthalocynine （Pc） Crystal. Due to the widely application of Pcs in the fields, such as the communication, medical treatment, chemical industry and so on, therefore, they have been a hot topic over several decades by scientists. Nowadays, scientists have prepared thousands of Pcs and their derivatives. However, along with the human society development and the progress in science and technology, the new phthalocyanine with novle characteristics are still the goal of the scientists. In this dissertion, the synthetic methods of the phthlocyanines are improved. Several novle phthalocyanines are prepared. In addition, the electroluminescent devices are fabricated based on these new materials.The synthesis and characterization of new unsymmetry substituted phthalocyanines: 2（3）-（p-tert-butylphenoxy） Phthalocyanine,2（3）-（ p-tert-butylphenoxy） copper Phthalocyanine, 2（3）-（p-tert-Butylphenoxy） Zinc Phthalocyanine, 2（3）,16（17）-di（p-tert-butylphenoxy） Phthalo -cyanine, 2（3）,16（17）-di（p-tert-Butylphenoxy） copper Phthalocyanine, 2（3）, 16 （17）-di（p -tert-butylphenoxy） Zinc Phthalocyanine, 2（3）,9（10）, 16（17）-tri（p-tert-butyl-phenoxy） Phtha -locyanine, 2（3）,9（10）, 16（17）-tri（p-tert -butylphenoxy） copper Phthalocyanine and 2（3）, 9（10）,16（17）-tri（p-tert -butylphenoxy） Zinc Phthalocyanine are described. The treatment of 4-（ p-tert-Butylphenoxy）phthalonitrile （A） , 1,3-diiminoisoindoline （B） and metallic salts [Cu（AcO）₂.2H₂O or Zn（AcO）₂.2H₂O] was added to organic solvent [1-pentanol, quinlonine and N,N-Dimethyl -formamide （DMF）] under stirring. Then, a catalytic amount of 1,8-Diazabicyclo [5,4,0]undec-7-ene （DBU） was added, and the mixture was heated under N2 for over 24 h. After cooling under N₂, anhydrous methanol was added into the reaction mixture to precipitate the solid and solvent was removed under reduced pressure. The collected solid powder were extracted with anhydrous methanol in a soxhlet extractor for 24 h and further purified twice by chromatography. The obtained unsymmetry substituted phthalocyanines were characterized by Mass spectrum （MS）, ultraviolet-visible （UV/Vis） spectrum, Infrared Spectroscopy （IR） and elemental analysis. The results are agreement with the proposed structures.A novel solvothermal synthesis method for direct preparing of crystals of copper （nickel） phthalocyanine is presented in this article. Using quinoline as solvent, crystals were prepared after cooling the reaction mixture to room temperature in autoclave. The three kind of starting materials which is using phthalonitrile, Cu（AcO）₂.2H₂O and NH₄MoO₄; 1, 3-diiminoisoindoline and Cu（AcO）₂.2H₂O; phthalonitrile, NH₄MoO₄ and CuO as starting materials, were preparing CuPc single crystals. The length of CuPc single crystals were 2 mm - 10.5 mm. These high quality crystals were suitable for X-ray poly crystalline diffraction （XRD） characterization. The molecular formula of CuPc is CuN₈C₃₂H₁₆, belong to monoclinic system, space group is P 2（l）/n, Unit cell parameters: a =14.668（3）, b= 4.8109（10）, c=19.515（7）,α=90,β= 121.04（2）,γ=90, cell volume is 1179.91 （?）³, According to the X-ray poly crystalline diffraction （XRD） spectrum, we can find that the position and the intensity of the diffraction peak were in conformity with the standard card, which proves that the crystals belong toβ-form crystalline. The influences of the different temperatures, reaction time and solvent volumes on the crystal yield were also discussed. We found that the highest CuPc crystal yield which using 1, 3-diiminoisoindoline and Cu（AcO）₂.2H₂O as starting materials was 52.3% under 270℃for 8 h in 10 ml quinoline.We for the first time using two kind of starting materials to synthesize single crystals of NiPc employed quinoline as solvent. The two kind of starting materials which is using phthalonitrile, Ni（AcO）₂.2H₂O and NH₄MoO₄; 1, 3-diiminoisbindoline, NH₄MoO₄ and Ni（AcO）₂.2H₂O as starting materials, were preparing single crystals of NiPc. The length of NiPc single crystals were also 2 mm-10.5 mm.These crystals were also suitable for XRD characterization. The molecular formula of ZnPc is ZnN₈C₃₂H₁₆, belong to monoclinic system, space group is P 2（1）/n, Unit cell parameters: a =14.668（3）, b= 4.8109（10）, c=19.515（7）,α=90,β=121.04（2）,γ=90, cell volume is 1173.6 （?）³, According to the X-ray poly crystalline diffraction （XRD） spectrum, we can find that the position and the intensity of the diffraction peak were in conformity with the standard card, which proves that the crystals belong toβ-form crystalline. To search for the optimum reaction for the highest crystal yield, and the highest NiPc crystal yield which using NH₄MoO₄; 1, 3-diiminoisoindoline and Ni（AcO）₂.2H₂O as starting materials was 56.84% under 270℃for 8 h in 14 ml quinoline.Moreover, this method may be easily applied in the crystal growth for other organic materials, and acts as an important method in scientific experiment. CuPc crystals, which are directly obtained using solvothermal synthesis, will be wildly used and produced in large quantities in industry in the near future.We fabricated OLEDs employing 2（3）-（ p-tert-butylphenoxy） copper Phthalocyanine, 2（3）,16（17）-di（p-tert-butyl-phenoxy） copper Phthalocyanine and 2（3）, 9（10）, 16（17）-tri （p-tert-butylphenoxy） copper Phthalocyanine as light emitting layer.The final structures of three-layer OLEDs based on 2（3）-（ p-tert-butylphenoxy） copper Phthalocyanine and 2（3）,9（10）, 16（17）-tri （p-tert-butylphenoxy） copper Phthalocyanine were ITO/NPB（40 nm）/Pc（30 nm）/AlQ（43.5 nm）/LiF （0.5 nm）/Al（120 nm） . Organic layers were deposited by vacuum (5.0-9.0×10^-4 Pa) thermal evaporation onto a clean glass substrate precoated with an indium tin oxide （ITO） layer with a sheet resistance of 100Ω/□and a transmittance of -80% in the measurement range. A 40-nm-thick film of N,N’-di-1-naphthyl-N,N’-diphenyl benzidine （NPB） was deposited as the hole-transport layer （HTL） at a deposition rate of 20 ?/min. Next, a 30-nm-thick Pc film was deposited as light emitting light emitting layer （LEL） at a deposition rate of 3 （?）/min（1 （?）/min）. Then, a 43.8-nm-thick layer of tris- （8-hydroxyquinoline） aluminum （Alq₃） was deposited as electron-transport layer and electron-inject layer at a deposition rate of 20 （?）/min. A 0.5-nm-thick LiF film was deposited as contact modification layer. Finally a shadow mask with 2×2 mm² openings was used to define the 120-nm-thick Al cathode. ITO, NPB, Alq₃ and A1 were used as anode, hole-transport layer, electron-transport layer and cathode respectively.The structure of three-layer OLED based on 2（3）,16（17）-di(p-tert-butyl-phenoxy copper Phthalocyanine was ITO/NPB（30 nm）/Pc（30 nm） /BCP（20 nm）/AlQ（30 nm）/LiF （0.5 nm）/Al（120 nm）. Organic layers were deposited by vacuum (5.0-9.0×10^-4 Pa) thermal evaporation onto a clean glass substrate precoated with an indium tin oxide （ITO） layer with a sheet resistance of 100Ω/□and a transmittance of -80% in the measurement range. A 30-nm-thick film of N,N’-di-1-naphthyl-N,N’-diphenyl benzidine （NPB） was deposited as the hole-transport layer （HTL） at a deposition rate of 20 （?）/min. Next, a 30-nm-thick Pc film was deposited as light emitting light emitting layer （LEL） at a deposition rate of 2 （?）/min. A 20-nm-thick 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline （BCP） was deposited as hole-blocking layer at a deposition rate of 15 （?）/min. Then, a 20-nm-thick layer of tris-（8-hydroxyquinoline） aluminum （Alq₃） was deposited as electron-transport layer and electron-inject layer at a deposition rate of 20 （?）/min. A 0.5-nm-thick LiF film was deposited as contact modification layer. Finally a shadow mask with 2×2 mm² openings was used to define the 120-nm-thick Al cathode. ITO, NPB, BCP, Alq₃ and Al were used as anode, hole-transport layer, hole-blocking layer, electron-transport layer and cathode respectively.Room-temperature electroluminescence was observed at about 869,1062; 1050,1110 and 1095,1204 nm for 2（3）-（ p-tert-butylphenoxy） copper Phthalocyanine , 2（3）, 16（ 17）- di(p-tert -butylphenoxy copper Phthalocyanine and 2（3）,9（10）, 16（17）-tri （p-tert-butylphenoxy） copper Phthalocyanine. The emission wavelengths and the half bandwidths were quite different for the phthalocyanine, which may be due to the differences of the number of substituted and the molecular aggregations in yacuum sublimed films. The difference of Stokes shift relaxation was also induced by the molecular aggregations.The synthesis and characterizations of Sub-Phthalocyanine copper are reported in this paper firstly. The mixture of 1,3-diiminoisoindoline and Cu（AcO）₂-2H₂O was added to quinoline under stirring. Then, a catalytic amount of DBU was added. The collected solid powder were extracted with anhydrous methanol in a soxhlet extractor and further purified by chromatography. Sub-Phthalocyanine copper is characterized by MS and elemental analysis. The results are agreement with the proposed structures. The Sub-phthalocyanine copper molecular was broken by laser which was shown in Mass Spectrum. We have analyzed this material decomposition process, and proposed the reaction mechanism through the broken of Sub- phthalocyanine copper molecular.更多还原