CN100365846C - Organic infrared photoelectric device and method for making same - Google Patents
Organic infrared photoelectric device and method for making same Download PDFInfo
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- CN100365846C CN100365846C CNB031110215A CN03111021A CN100365846C CN 100365846 C CN100365846 C CN 100365846C CN B031110215 A CNB031110215 A CN B031110215A CN 03111021 A CN03111021 A CN 03111021A CN 100365846 C CN100365846 C CN 100365846C
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Abstract
The present invention relates to an organic infrared photoelectric device and a preparation method of the device based on metal phthalocyanin compound of a super large ring. Organic infrared photoelectric device is composed of a glass or a flexible transparent substrata (1), a low electrode (2) of a transparent or semitransparent film, an organic/polymer photoactive layer (3) and an upper electrode (4) of a metal film, wherein the organic / polymer photoactive layer (3) is obtained by a quartz boat or a molybdenum boat heating the metal phthalocyanine compound of the super large ring to be thermally evaporated; the temperature of the thermal evaporation is from 600 DEG to 900 DEG; the metal phthalocyanine compound of the super large ring can be dissolved into the solution of Dimethyl Sulphoxide (DMSO) and coated in a spin way onto ITO glass, and the metal phthalocyanine compound can be obtained under the condition that an ordinary mechanical pump can reach a low vacuum state. The photoelectric device prepared by the present invention has good photovoltaic response characteristics in the wavelength region from 0.9 microns to 1.6 microns in an infrared area, and good infrared light can be emitted in the wavelength range from 1.5 microns to 1.6 microns.
Description
Technical field:
The present invention relates to a kind of organic electro-optic device and preparation method thereof, specifically relate to a kind of organic infrared electro device and this preparation of devices method based on super large ring metal phthalocyanine material.
Background technology:
Organic electro-optic device includes organic electroluminescence devices, solar cell, photoelectricity testing part and photovoltaic device etc.Because characteristics such as organic material has that cost is low, light weight, volume are little, can be processed into arbitrary shape, suit to be processed into the large-area flat-plate device, also can to process on flexible substrate, thereby organic electro-optic device has very important application in fields such as information, the energy, military affairs, becomes the research focus of present international and domestic academia.Existing organic electro-optic device generally is the multi-layer film structure photoelectric device on glass substrate or the flexible and transparent organic film substrate.The simplest device architecture is three-layer thin-film structure (seeing accompanying drawing 1 and description of drawings), and device architecture is followed successively by glass (or flexible and transparent organic film) substrate (1), transparent (or translucent) electrode (2), organic polymer photoactive layer (3) and film top electrode (4) from bottom to top.But general organic polymer material does not have photolytic activity at the region of ultra-red greater than 1 micron wave length scope, therefore pure organic materials up to the present also of no use is made greater than 1 micron wave length, particularly the infrared light-emitting device of 1.5 micron optical fiber communication bands and light detecting device and photronic report.The equal non-refractory of organic polymer material that simultaneously present photoactive layer uses, material just can decompose or distil down at 200～500 ℃ generally speaking.
Summary of the invention:
Purpose of the present invention is exactly in order to overcome these difficulties in the prior art, with use band extension to 1.5～1.6 of organic polymer photoelectric device micron, improve the resistance to elevated temperatures of device, thereby a kind of infrared electro device and this preparation of devices method based on super large ring metal phthalocyanine organic active layer is provided.
Know-why of the present invention is based on the super large ring metal phthalocyanine new material that has 6 isoindole structure subunits in the synthetic recently class porphyrazine ring of our seminar, the structure of this phthalocyanine material and concrete preparation method see the patent of invention that we applied for to Patent Office of the People's Republic of China on February 11st, 2003 for details: " the super-phthalocyanine compound, synthetic method and the purposes that have 6 isoindole structure subunits in the porphyrazine ring ", number of patent application: 03110994.2.Synthetic first and find that first kind of phthalocyanine organic compound structure is over 100 years since people in 1907, the phthalocyanine of existing more than 5,000 kind of different structure is synthesized and makes, but the phthalocyanine of these several thousand kinds of different structures all is by accompanying drawing 2 (a), (b), the phthalocyanine basic structure of molecular structure (c) derives out, and these three phthalocyanine molecular structures the most basic are the inferior phthalocyanine structure＜Fig. 2 (a) with three iso-indoles subunit porphyrazine rings 〉, phthalocyanine structure＜Fig. 2 (b) with porphyrazine ring of four iso-indoles subunits〉and have super phthalocyanine structure＜Fig. 2 (c) of five iso-indoles subunit porphyrazine rings 〉.Recently, we have synthesized a series of azepine metal phthalocyanines (being called for short super large ring metal phthalocyanine later on) with 6 isoindole structure subunit porphyrazine rings, its molecular structure is shown in Fig. 2 (d), and this is the 4th basic structure of phthalocyanine extended familys, also is the 4th branch family of phthalocyanine extended familys.Metal shown in Fig. 2 (d) is copper (Cu), our also synthetic making of this super large ring metal phthalocyanine of other metallic element (as cobalt, iron, zinc etc.), about this class super large ring metal phthalocyanine synthesis technique and structure referring to patent 03110994.2.To the further investigation of this class super large ring metal phthalocyanine characteristic, we find because the expansion of porphyrazine ring, and the embedding of two metallic atoms, this class super large ring metal phthalocyanine has photolytic activity at wavelength greater than 1.4～1.6 microns infrared bands of 1 micron.Accompanying drawing 3 (a) and (b), (c) show optical absorption spectra, infrared light fluorescence Spectra and the photovoltaic spectrum of this super large ring metal phthalocyanine dusty material or thin-film material respectively.We find that also the super large ring metal phthalocyanine material of this new construction has good thermal stability simultaneously, are under the 10-3-10-4Pa condition in vacuum degree, and decomposition temperature is about 1000 ℃.In view of the above, we have developed the photoelectric device of the present invention based on super large ring metal phthalocyanine made related in the patent 03110994.2.The designed photoelectric device of the present invention is made of glass substrate (1), ito transparent electrode (2), organic photoactive layer (3), top electrode (4), the invention is characterized in that photoactive layer (3) is to be made of super large ring metal phthalocyanine material.
The present invention compares with existing organic polymer photoelectric device, uses band extension to the 1.4-1.6 micron, and this is the applied wave band of optical-fibre communications just, and therefore, proposition of the present invention has been opened up road for organic electro-optic device enters the optical-fibre communications application.Infrared band also is the wave band that important application is arranged in the military affairs, and the present invention also will make organic electro-optic device militarily bring into play bigger effect, but the present invention simultaneously is than the temperature of existing organic polymer photoelectric device Nai Genggao.
Description of drawings:
Fig. 1: three-layer thin-film structure organic electro-optic device schematic diagram;
Fig. 2: several phthalocyanine basic structure molecular formula;
(a) inferior phthalocyanine molecular structure, (b) phthalocyanine molecular structure,
(c) super phthalocyanine molecular structure, (d) super large ring metal phthalocyanine molecular structure.
Fig. 3: the photolytic activity spectrogram of super large ring metal phthalocyanine material;
(a) powder formic acid solution optical absorption spectra, (b) thin-film material infrared light fluorescence Spectra,
(c) dusty material infrared light voltage spectrum;
Fig. 4: four-level membrane structure organic electro-optic device schematic diagram;
Fig. 5: five layer film structure organic electro-optic device schematic diagrames;
Fig. 6: three-layer thin-film structure organic luminescent device output spectrum figure;
Fig. 7. three-layer thin-film structure organic photovoltaic devices output photovoltage is schemed medium and small illustration for exporting photovoltage with incident light source laser wavelength change curve with incident light source laser power conversion curve figure.
Value when curve a, b, c are respectively 1510nm, 1550nm, 1590nm for the incident light source laser wavelength among the figure.
Parts among Fig. 1,4,5 (1) are glass (or flexible and transparent organic film) substrate, and (2) are transparent (or translucent) electrode, are generally the ITO film of ito glass, and (3) are the organic polymer photoactive layer, and (4) are aluminium film top electrode.Parts among Fig. 4, Fig. 5 (5) are electron transfer layer.Parts among Fig. 5 (6) are hole transmission layer.
Embodiment:
This optoelectronic device structure as shown in Figure 1.Implementing process is summarized as follows: selecting electro-conductive glass (ito glass) for use is substrate (1), and the ito thin film on it is bottom electrode (2), in vacuum 10
-4Under the Pa condition, carry out thermal evaporation with quartz boat or molybdenum boat heating super large ring metal phthalocyanine, go up preparation photoactive layer (3) at bottom electrode (2), the thermal evaporation temperature is 600-900 ℃; Also can prepare super large ring metal phthalocyanine photoactive layer (3) with spin-coating method, concrete grammar is that super large ring metal phthalocyanine is dissolved in diformazan Ya Ji Sulfone (DMSO) solution, be spun on the ito glass, the baking drying is prepared into super large ring metal phthalocyanine film light active layer (3) under the low vacuum condition that the standard machinery pump can reach then, goes up evaporation aluminium film top electrode (4) at photoactive layer (3) at last.The electroluminescent device of this three-layer thin-film structure, solar cell and photovoltaic device structure all are the same.
This optoelectronic device structure as shown in Figure 4.This device architecture is on the basis of three-layer thin-film structure organic electro-optic device as shown in Figure 1, adds one deck electron transfer layer (5) between super large ring metal phthalocyanine photoactive layer (3) and aluminium film top electrode (4).The three-layer thin-film structure organic electro-optic device of concrete technology and embodiment 1 is identical, super large ring metal phthalocyanine photoactive layer (3) and electron transfer layer (5) be can prepare with the method for thermal evaporation, also can super large ring metal phthalocyanine photoactive layer (3) and electron transfer layer (5) be prepared with spin-coating method.The material of electron transfer layer (5) can be selected the electric transmission layer material of existing organic polymer photoelectric device for use.But, the structure of the electroluminescent device of this four-level membrane structure and solar cell, photovoltaic device is different: the electroluminescent device structure as shown in Figure 4, electron transfer layer (5) is positioned between super large ring metal phthalocyanine photoactive layer (3) and the aluminium film top electrode (4); And solar cell and photovoltaic device electron transfer layer (5) are positioned between super large ring metal phthalocyanine photoactive layer (3) and the ito thin film bottom electrode (2).
This optoelectronic device structure as shown in Figure 5.This device architecture is on the basis of four-level membrane structure organic electro-optic device as shown in Figure 4, adds one deck hole transmission layer (6) between super large ring metal phthalocyanine photoactive layer (3) and ito thin film bottom electrode (2).The four-level membrane structure organic electro-optic device of concrete technology and embodiment 2 is identical, super large ring metal phthalocyanine photoactive layer (3), electron transfer layer (5) and hole transmission layer (6) be can prepare with the method for thermal evaporation, also can super large ring metal phthalocyanine photoactive layer (3), electron transfer layer (5) and hole transmission layer (6) be prepared with spin-coating method.The material of electron transfer layer (5) and hole transmission layer (6) can be selected the electron transfer layer and the hole transport layer material of existing organic polymer photoelectric device for use.The structure of the electroluminescent device of this five layer film structures and solar cell, photovoltaic device also is different: the electroluminescent device structure as shown in Figure 5, electron transfer layer (5) is positioned between super large ring metal phthalocyanine photoactive layer (3) and the aluminium film top electrode (4), and hole transmission layer (6) is positioned at super large ring metal phthalocyanine photoactive layer (3) and ito thin film is between the bottom electrode (2); And solar cell and photovoltaic device electron transfer layer (5) are positioned between super large ring metal phthalocyanine photoactive layer (3) and the ito thin film bottom electrode (2), and hole transmission layer (6) is positioned between super large ring metal phthalocyanine photoactive layer (3) and the aluminium film top electrode (4).
The photoactive layer material that fabricate devices is used in electric transmission layer material, hole transport layer material and the background technology described in the embodiment of the invention can be " semiconductor laser device physics " (publishing house of Jilin University, publish in May, 2002, ISBN7-5601-2648-0/TN-10) the cited several representative materials of 294-296 page or leaf, or be that present technique field those of ordinary skill is engaged in material commonly used in the photoelectric device preparation process.
With reference to the accompanying drawings 6, accompanying drawing 7, the performance test of the organic infrared photovoltaic device of super large ring metal phthalocyanine of our development is at present shown: this kind device all has good photovoltaic response characteristic in infrared region 0.9～1.6 micron wave length scope; Performance test to the present organic infrared light-emitting device of super large ring metal phthalocyanine that we develop shows: this kind device has good infrared light to send in 1.5～1.6 micron wave length scopes, and this wave-length coverage just in time is the main wave band of present optical-fibre communications.
From embodiment 1～3 as can be seen, the critical process of the organic infrared electro device of preparation super large ring metal phthalocyanine is the preparation of super large ring metal phthalocyanine photoactive layer (3), and its process conditions are: in vacuum 10
-4Under the Pa condition, carry out prepared by heat evaporation photoactive layer (3) with quartz boat or molybdenum boat heating super large ring metal phthalocyanine, the thermal evaporation temperature is 600-900 ℃; Also can prepare super large ring metal phthalocyanine photoactive layer (3) with spin-coating method, concrete grammar is that super large ring metal phthalocyanine is dissolved in diformazan Ya Ji Sulfone (DMSO) solution, be spun on the ito glass, the baking drying is prepared into super large ring metal phthalocyanine film light active layer (3) under the low vacuum condition that the standard machinery pump can reach then.
Claims (6)
1. organic infrared electro device, be made up of glass or flexible transparent substrate (1), transparent or semitransparent film bottom electrode (2), organic polymer photoactive layer (3) and metallic film top electrode (4), it is characterized in that: organic polymer photoactive layer (3) is to be prepared from by super large ring metal phthalocyanine organic material.
2. organic infrared electro device as claimed in claim 1, it is characterized in that: at organic polymer is to also have electron transfer layer (5) between super large ring metal phthalocyanine photoactive layer (3) and the metallic film top electrode (4), thereby constitutes a kind of organic luminescent device of four-level membrane structure.
3. organic infrared electro device as claimed in claim 2, it is characterized in that: between super large ring metal phthalocyanine photoactive layer (3) and transparent or semitransparent film bottom electrode (2), also have hole transmission layer (6), thereby constitute a kind of organic luminescent device of five layer film structures.
4. organic infrared electro device as claimed in claim 1, it is characterized in that: between transparent or semitransparent film bottom electrode (2) and super large ring metal phthalocyanine photoactive layer (3), also have electron transfer layer (5), thereby constitute a kind of organic photovoltaic devices of four-level membrane structure.
5. organic infrared electro device as claimed in claim 4, it is characterized in that: between super large ring metal phthalocyanine photoactive layer (3) and transparent or semitransparent film bottom electrode (2), also have hole transmission layer (6), thereby constitute a kind of organic photovoltaic devices of five layer film structures.
6. method for preparing organic infrared electro device as claimed in claim 1, step is the transparent or semitransparent film bottom electrode of evaporation (2), organic polymer photoactive layer (3) and a metallic film top electrode (4) successively on substrate (1), and it is characterized in that: the evaporation of organic polymer photoactive layer (3) is in vacuum 10
-4Under the Pa condition, carry out thermal evaporation with quartz boat or molybdenum boat heating super large ring metal phthalocyanine material, the thermal evaporation temperature is 600-900 ℃.
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| CN102867921B (en) * | 2012-09-13 | 2015-11-25 | 深圳市华星光电技术有限公司 | Organic display device |
| CN107039603A (en) * | 2017-04-18 | 2017-08-11 | 哈尔滨理工大学 | The preparation of ZnPc/PbPc blending evaporated film diodes and working characteristics |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN2291695Y (en) * | 1996-04-04 | 1998-09-16 | 张志林 | Long-life organic thin-film electroluminescent screen |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN2291695Y (en) * | 1996-04-04 | 1998-09-16 | 张志林 | Long-life organic thin-film electroluminescent screen |
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