脂肪醇甲酸酯类酞菁铜配合物的合成、表征及荧光性能

报道了四甲酰氯酞菁铜的合成及其与反应得到正丁醇、正戊醇、正己醇、正辛醇、正十二醇5个含脂肪链取代基的酞菁铜衍生物.分别用红外光谱、紫外-可见光谱、元素分析、核磁共振氢谱等方法对这些衍生物进行了结构和取代度的表征,并研究了该系列酞菁铜衍生物在有机溶剂中的溶解性及荧光性能与浓度、取代基的关系.研究结果表明在一般有机溶剂中这些酞菁铜衍生物的溶解性显著提高,荧光强度不随浓度的变化而线性变化、长链要高于短链取代酞菁铜衍生物的荧光强度.     

C60-甲苯衍生物对酞菁铜/C60薄膜光电性能的影响

从光电导－时间关系，瞬态光电导能谱和光诱导放电曲线（PIDC）等方面研究C60－甲苯衍生物对酞菁铜（CuPc)/C60薄膜光电性能的影响，并对其机理进行了探讨，C60－甲苯衍生物对C60－甲苯衍生物／CuPc/C60多层膜的光电性能具有明显的增强效应。     

二烷氧基取代酞菁的合成及其吸收光谱的研究

以1,3,3-三氯异二氢氮杂茚和3-(2’,2’,4’-三甲基-3’-戊氧基)-1,3-二亚胺基异吲哚啉为原料,合成了二烷氧基取代无金属酞菁,产物经IR,UV-Vis,1H NMR及MS表征。在与相应的四烷氧基取代无金属酞菁相比较的基础上,探讨了产物的UV-Vis光谱中的Q带波长及其分裂程度与取代基的数目以及溶剂极性的关系。     

酞菁铜薄膜的光记录特性

研究了有机染料酞菁铜（ＣｕＰｃ）真空蒸镀薄膜在可见及近红外区域的吸收光谱和光学常数，发现酞菁铜薄膜在５５０－７５０ｎｍ波长范围内具有较强的吸收，在静态测试仪上测试了酞菁铜薄膜的光存储记录特性，发现用低功率氦氖激光照样品时薄膜反射率变化较大，在酞菁记录层上覆盖金属反射层将提高写入激光的阈值能量并且增大反射率的对比度。     

新型八取代酞菁谱学性质研究

对1,4,8,11,15,18,22,25-八氧代正丁基酞菁铜、1,4,8,11,15,18,22,25-八氧代丁酸甲酯基酞菁锰、1,4,8,11,15,18,22,25-八氧代正丁酸甲酯基酞菁铜、1,4,8,11,15,18,22,25-八氧代正丁酸甲酯基酞菁锌这四种新型八取代酞菁的红外光谱、紫外光谱和荧光光谱的性质...     

固态和液态溶液中酞菁铜及其衍生物的光谱变化

研究了三种酞菁铜及其衍生物CuPc,tb-CuPc,oo-CuPc在不同环境状态下的吸收光谱的变化。讨论了三种被质子化前后在溶液中的吸收光谱Q带的红移机制,并与固体分散样品所产生的光谱进行了比较,研究了酞菁铜衍生物分散在聚合物薄膜样品分子间的相互作用导致的吸收光谱的改变。同时结合POM,DSC,XRD方法,进一步对薄膜材料的结构和物相进行了表征。结果表明在不同浓度酞菁铜衍生物掺杂的固体薄膜中,被分散的酞菁铜衍生物的分子之间仍然处于缔合或凝聚状态,降低酞菁铜衍生物掺杂浓度并不能解除缔合作用或改变固体薄膜样品中的吸收光谱。     

亚酞菁薄膜的折射率和吸收特性

通过真空镀膜法在单晶硅片上制备了一种新的严酞菁（三硝基溴硼亚酞菁）薄膜,利用全自动椭圆偏振光谱仪研究了该薄膜的椭偏光谱,测量了其复折射率,复介电常数和吸收系数,估算了薄膜在窗口区域的俘获能级并对其吸收谱的成因作了分析。     

1,11,15,25-四羟基-4,8,18,22-二（桥联二丙羧基）酞菁铜的合成及性质研究

对新型取代基酞菁和酞菁晶体合成和性质进行了研究。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,合成了新型的桥联酞菁材料：1,11,15,25-四羟基-4,8,18,22-二（桥联二丙羧基）酞菁铜,表征其结构。并研究电化学性质。首先以丙二酸和3,6-二羟基邻苯二腈为起始原料,以水为溶剂,加入浓硫酸作为催化剂,先合成前体,即丙二酸3,3′-二(6–羟基邻苯二腈)脂。然后再用丙二酸 3,3′-二(6-羟基邻苯二腈)脂与一水合乙酸铜,以正戊醇为溶剂,以DBU为催化剂,合成了1,11,15,25-四羟基-4,8,18,22-二（桥联二丙羧基）酞菁铜,其分子式是C₃₈H₁₆N₈O₁₂Cu。对1,11,15,25-四羟基-4,8,18,22–二（桥联二丙羧基）酞菁铜进行紫外吸收及荧光光谱测定,证明合成产物是目标产物,并研究了1,11,15,25-四羟基-4,8,18,22-二（桥联二丙羧基）酞菁铜的电化学性质。     

酞菁铜固态薄膜的红外光谱

利用红外透射光谱，偏振透射光谱、掠角反射光谱研究了三－２，４－二特戊基苯氧基８－喹啉氧基酞菁铜ＬＢ膜和蒸镀膜的结构。确认在ＬＢ膜中，（１）取代基的碳链是以六方晶系或假六方晶系方式堆积的；（２）用偏振红外可以区别苯环上的两个ＣＨ２的伸缩振动带。在蒸镀膜中分子基本呈现无序状态。     

亚酞菁薄膜的光谱和光存储性质研究

利用真空蒸镀法制备了一种新的三硝基溴硼亚酞菁（BTN－SubPc)薄膜。在室温下测试了该亚酞菁染料在溶液和薄膜态的吸收光谱、薄膜态的反射和透过光谱，发现该薄膜在500nm-650nm波长范围内具有优良的吸收和反射特性。在632.8nm光盘静态测试仪上测试了覆盖有金属反射层的BTN－SubPc薄膜的静态光存储性能，结果表明，用较小功率和较窄脉宽的激光辐照膜片时，可获得大于30％的反射率对比度，显示出该材料用作短波长光存储介质（特别是用于可录型数字多用光盘）的巨大潜力。     

酞菁铜旋涂薄膜的形貌与光谱学性质研究

采用旋涂法制备了2,9,16,23-四-异丙氧基酞菁铜(CuPc(OC3H7-i)4)薄膜,利用AFM、UV-Vis和FT-IR对薄膜的表面形貌和光谱学性质进行了表征。薄膜表面结构是由约为216nm×55nm×4nm的清晰纳米畴组成,旋涂膜中酞菁铜分子是处于一种无序的状态,其Soret带吸收与氯仿溶液相比位置不变,而Q带的聚集体和单体的吸收峰红移约20nm。     

Optical characterization of bromo-alkoxyl-substituted copper phthalocyanine derivative thin films

A series of thin films of copper phthalocyanine derivatives with bromine and alkoxyl substituents [CuPc(OC₈H₁₇)₄Br_m, m=0,1,2,4] were prepared on single-crystal silicon substrates by spin coating. The ellipsometric spectra of the films have been studied on a rotating analyzer–polarizer type of scanning ellipsometer. The optical, dielectric constants and absorption coefficients of the films in 500–800 nm wavelength region were obtained. The results show that the complex refractive index, dielectric constants and absorption coefficient of these thin films are influenced regularly by bromine substituent on conjugated macrocycle. It was found that there are approximately linear relationships between the resonance absorption wavelengths of the films and the average number of bromine atoms substituted on the phthalocyanine ring.     

酞菁铜衍生物在酞菁酮—氧化铁纳米粒子交替LB膜中的分子取向

通过Langmuir-Blodett技术制备了酞菁酮－氧化铁纳米粒子交替LB膜,利用偏振紫外－可见光谱对酞菁铜衍生物在不同制膜条件下所制得的交替膜中的分子取向进行了研究。结果表明,在同一氧化铁溶胶亚相中,随着表面压的增大,或在相同的表面压下,随着亚相中氧化铁浓度的减小,酞菁铜分子在其复合LB膜中倾斜程度变大。     

新型不对称酞菁的电致发光性质研究

制作了以3种新璎不对称酞菁铜为发光层的电致发光器件并研究了其电致发光性质.3种新型不对称酞菁铜为2(3)-(对叔丁基苯氧基)酞菁铜(1),2(3),9(10),16(17)-三-(对叔丁基苯氧基)酞菁铜(2)和2(3),16(17)-二-(对叔丁基苯氧基)酞菁铜(3).其中以(1)和(3)为发光层的器件结构ITO/NPB(40 nm)/Phthalocynine(Pc)(30 nm)/AlQ(43.8 nm)/LiF(0.5 nm)/Al(120 nm).其中以(2)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).以(1),(2)和(3)为发光层与Q带栩关联的发射波长分别出现在869和1 062 nm;1 050和1110 nm;和1 095和1 204 nm.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3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.     

LB薄膜中四新戊氧基酞菁锌和四壬基酞菁铜分子聚集体的吸收光谱的温度特性

本文制备了四新戊氧基酞菁锌(Tetra-neopentoxy phthalocyanine zine)(TNPPeZn)和四壬基酞菁铜(Tetra-nonyl phthalocyanine copper)(TNPeCu)两种酞菁衍生物的Langmuir-Blodgett(LB)薄膜.通过测量10～473K温度下的吸收光谱,研究了两种薄膜的分子聚集状态.TNPPeZn的LB薄膜中,存在着分子单体和分子二聚体,在吸收光谱中分别表现为680nm和620nm的吸收峰.随着温度的升高,分子单体逐渐转变为分子二聚体,这个过程是不可逆的.TNPeCu的LB薄膜中,除了分子单体和分子二聚体以外,还有吸收为740nm的分子J聚集体存在.随着温度的变化,J聚集体发生可逆变化.     

Structure and morphology of CuPc and F16CuPc pn heterojunction

This article reports structure and morphology of copper phthalocyanine (CuPc) and fluorinated copper phthalocyanine (F₁₆CuPc) pn heterojunction. Highly ordered CuPc and F₁₆CuPc polycrystalline thin films with the 2 0 0 plane spacing s of 1.30 and 1.56 nm, respectively, could be continuously grown via an intermediate-phase layer. Compared with CuPc, the intermediate-phase layer is much thinner when F₁₆CuPc is used as the first layer. The rougher the first layer is, the thicker the intermediate-phase layer is. Similarly, the 2 0 0 plane spacings of the intermediate-phase layer are dependent on morphology of the first layer. Furthermore, morphology of the heterostructure is mainly dominated by that of CuPc films. Due to the thicker intermediate-phase layer in the CuPc/F₁₆CuPc heterostructure, the thin film transistors (TFT) performance is obviously inferior to that of the F₁₆CuPc/CuPc device.     

Influence of the molecular structure of copper phthalocyanines on their ordering in thin films and photoluminescence and absorption spectra

Thin films consisting of copper phthalocyanine (CuPc) molecules and copper phthalocyanine molecular complexes with different structures on glass and glass-ceramic substrates are studied using reflectance anisotropy, photoluminescence, and photoconductivity (constant photocurrent method) spectroscopies. It is established that, in the studied films, the CuPc molecules and CuPc molecules containing peripheral phthalimide substituents are located in planes virtually parallel to the surface of the substrate. In thin films consisting of μ-peroxo dimer complexes, the angle between the CuPc molecular planes and the surface of the substrate is close to 90°. The thin films formed by CuPc molecules containing peripheral phthalimide substituents are characterized by the highest luminescence intensity in the range of ～ 1.12 eV and the lowest absorption intensity in the range of energies less than the band gap. These properties are explained by the lower concentration of non-radiative recombination centers in the film.     

Morphological control of copper phthalocyanine films by protonation-electrophoretic deposition

Films composed of various nanostructured copper phthalocyanine are controllably prepared by the method of protonation-electrophoretic deposition. The ultralong nanowires of copper phthalocyanine are grown at the deposition temperature of 70 °C. And the results of films UV-vis absorption spectra and X-ray diffraction indicate that copper phthalocyanine possesses the transformation tendency from α-phase to thermostable β-phase under the higher deposition temperature. The formation process of the ultralong nanowires illustrates that the nanowires grow in longitudinal orientation much faster than in lateral direction. And the time dependence of the films morphology, from another point of view, proves that copper phthalocyanine is dissolved in the precursor solutions, and the formation of the nanostructured copper phthalocyanine contains the process of crystal growth, which is different from the traditional electrophoretic deposition. So the films morphology is flexible to be controlled by varying the deposition conditions. These diverse nanostructured films have potential applications in the electrochemical and optoelectrical equipments.     

Laser-driven metal exchange and preparation of metal phthalocyanine

Two types of laser-driven dry processes for the preparation of metal phthalocyanine are reported. In the first one, laser-driven metal exchange, the excimer laser beam was focused on a copper target, and ablated copper atoms were injected onto a thin film of dilithium phthalocyanine (Li₂Pc). The central metal atoms of Li₂Pc were partially exchanged by copper atoms, and the blue thin film of copper phthalocyanine (CuPc) was obtained after removal of the residual Li₂Pc by the hydrochloric acid treatment. In the second one, direct synthesis using the component organic molecule, CuPc was prepared by the implantation of laser-ablated copper atoms onto a thin film of 1,3-diiminoisoindoline (D I I I).     

Thin films prepared by simultaneous deposition of copper and free-base phthalocyanine

Composite films of metals and dielectrics attracted considerable attention in the past for their novel optical and mechanical properties which can be tailored precisely by changing their structure and composition. In this work we present a probe into a related but hitherto unexplored field of composites where metal is combined with molecular semiconductor. As model materials we chose free-base phthalocyanine and copper. Films were prepared by simultaneous deposition of copper and free-base phthalocyanine in the dual ICB system. An answer to two basic questions was sought after: 1) does the copper combine with freebase phthalocyanine to form a copper phthalocyanine complex, 2) what is the structure of the films if there is non-stoichiometric surplus of copper in the films? We report results of structural study by a transmission electron microscope. Optical behaviour of the composite was characterized by optical reflectance and transmittance measurement in UV/VIS/NIR range and complemented by FT IR spectra.