CN100365846C - Organic infrared photoelectric device and its preparation method - Google Patents

Abstract

The invention relates to an organic infrared photoelectric device based on a supermacrocyclic metal phthalocyanine compound and a preparation method of the device. The organic photoelectric device consists of a glass or flexible transparent substrate (1), a transparent or translucent thin film lower electrode (2), an organic polymer photoactive layer (3) and a metal thin film upper electrode (4). Wherein the organic polymer photoactive layer (3) is obtained by heating supermacrocyclic metal phthalocyanine compound with quartz boat or molybdenum boat under the condition of vacuum 10 ^-4 Pa for thermal evaporation, and the thermal evaporation temperature is 600-900°C; The supermacrocyclic metal phthalocyanine compound is dissolved in dimethyl ethylene sulfone (DMSO) solution, spin-coated on ITO glass, and then baked and dried under low vacuum conditions that can be achieved by ordinary mechanical pumps. The photoelectric device prepared by the invention has good photovoltaic response characteristics in the wavelength range of 0.9-1.6 microns in the infrared region, and has good infrared light emission in the wavelength range of 1.5-1.6 microns.

Description

Organic infrared photoelectric device and its preparation method

Technical field:

The invention relates to an organic photoelectric device and a preparation method thereof, in particular to an organic infrared photoelectric device based on a supermacrocyclic metal phthalocyanine material and a preparation method of the device.

Background technique:

Organic optoelectronic devices include organic electroluminescent devices, solar cells, photodetection devices, and photovoltaic devices. Because organic materials have the characteristics of low cost, light weight, and small size, they can be processed into arbitrary shapes, suitable for processing into large-area flat-panel devices, and can also be processed on flexible substrates. Therefore, organic optoelectronic devices are widely used in information, energy, military and other fields. It has a very important application and has become a research hotspot in the international and domestic academic circles. Existing organic optoelectronic devices are generally multilayer thin film structure optoelectronic devices on glass substrates or flexible transparent organic thin film substrates. The simplest device structure is a three-layer thin film structure (see accompanying drawing 1 and accompanying drawing description), and the device structure is successively from bottom to top glass (or flexible transparent organic film) substrate (1), transparent (or translucent) electrode ( 2), an organic polymer photoactive layer (3) and a film upper electrode (4). However, general organic polymer materials have no photoactivity in the infrared region with a wavelength greater than 1 micron, so so far no infrared light-emitting devices and photodetectors with wavelengths greater than 1 micron, especially 1.5 micron optical fiber communication bands, have been made with pure organic materials. Reports on devices and photovoltaic cells. At the same time, the organic polymer materials currently used in the photoactive layer are not resistant to high temperatures, and generally the materials can be decomposed or sublimated at 200-500°C.

Invention content:

The purpose of the present invention is to overcome these difficulties in the prior art, extend the use band of organic polymer photoelectric devices to 1.5-1.6 microns, improve the high temperature resistance performance of the device, thereby provide a kind of organic activity based on super-macrocyclic metal phthalocyanine Layer infrared optoelectronic device and its preparation method.

The technical principle of the present invention is based on a new super-macrocyclic metallophthalocyanine material with 6 isoindole structural subunits in a class of porphyrazine ring recently synthesized by our research group. The structure and specific preparation method of the phthalocyanine material are detailed in our Invention patent applied to China Patent Office on February 11, 2003: "Super phthalocyanine compound with 6 isoindole structural subunits in the porphyrazine ring, synthesis method and application", patent application number: 03110994.2. Since people first synthesized and discovered the structure of the first phthalocyanine organic compound in 1907, more than 5,000 phthalocyanines with different structures have been synthesized and prepared, but these thousands of phthalocyanines with different structures are obtained from the attached Figure 2 (a), (b), (c) derived from the basic structure of the phthalocyanine molecular structure shown in (c), these three most basic phthalocyanine molecular structure is a subunit with three isoindole subunit porphyrazine ring Phthalocyanine structure <Fig. 2(a)>, a phthalocyanine structure with a porphyrazine ring with four isoindole subunits <Fig. 2(b)>, and a superphthalocyanine with a porphyrazine ring with five isoindole subunits Structure <Fig. 2(c)>. Recently, we have synthesized a series of azametallophthalocyanines with six isoindole structural subunit porphyrazine rings (hereafter referred to as supermacrocyclic metallophthalocyanines), whose molecular structure is shown in Figure 2(d). The fourth basic structure of the cyanine family is also the fourth branch of the phthalocyanine family. The metal shown in Figure 2(d) is copper (Cu), and we have also synthesized this super-large ring metallophthalocyanine of other metal elements (such as cobalt, iron, zinc, etc.). For the synthesis process and structure of cyanine, refer to patent 03110994.2. In-depth research on the characteristics of this type of super-large ring metal phthalocyanine, we found that due to the expansion of the porphyrazine ring and the embedding of two metal atoms, this type of super-large ring metal phthalocyanine has a wavelength greater than 1 micron in the 1.4-1.6 micron infrared band. photoactive. Accompanying drawing 3 (a), (b), (c) respectively show the light absorption spectrum, infrared light fluorescence spectrum and photovoltage spectrum of this supermacrocyclic metal phthalocyanine powder material or thin film material. At the same time, we also found that this super-large ring metal phthalocyanine material with a new structure has good thermal stability, and the decomposition temperature is about 1000 °C under the condition of vacuum degree of 10-3-10-4Pa. Accordingly, we have developed the optoelectronic device of the present invention based on the supermacrocyclic metallophthalocyanine material involved in the patent 03110994.2. The optoelectronic device designed by the present invention is made of glass substrate (1), ITO transparent electrode (2), organic photoactive layer (3), upper electrode (4), and the present invention is characterized in that photoactive layer (3) is made of Super macrocyclic metal phthalocyanine materials.

Compared with the existing organic polymer optoelectronic devices, the present invention uses a wave band extended to 1.4-1.6 microns, which is the wave band used in optical fiber communication. Therefore, the proposal of the present invention opens up a new era for organic optoelectronic devices to enter the field of optical fiber communication applications. the way. The infrared band is also an important band for military applications. The invention will also make the organic optoelectronic devices play a greater role in the military. At the same time, the invention can withstand higher temperatures than the existing organic polymer optoelectronic devices.

Description of drawings:

Figure 1: Schematic diagram of an organic optoelectronic device with a three-layer thin film structure;

Figure 2: The basic structural molecular formula of several phthalocyanines;

(a) molecular structure of subphthalocyanine, (b) molecular structure of phthalocyanine,

(c) Molecular structure of superphthalocyanine, (d) Molecular structure of supermacrocyclic metallophthalocyanine.

Figure 3: Photoactivity spectrum of super-macrocyclic metal phthalocyanine materials;

(a) Absorption spectrum of powdered formic acid solution, (b) Infrared fluorescence spectrum of film material,

(c) Infrared photovoltage spectrum of powder materials;

Figure 4: Schematic diagram of an organic optoelectronic device with a four-layer thin film structure;

Figure 5: Schematic diagram of organic optoelectronic device with five-layer thin film structure;

Figure 6: The output spectrum of an organic light-emitting device with a three-layer thin film structure;

Figure 7. The output photovoltage of the organic photovoltaic device with three-layer thin film structure and the power conversion curve of the incident light source laser. The small insert in the figure is the change curve of the output photovoltage with the wavelength of the incident light source laser.

Curves a, b, and c in the figure are the values when the wavelength of the incident light source laser is 1510nm, 1550nm, and 1590nm respectively.

Components (1) in Figures 1, 4, and 5 are glass (or flexible transparent organic film) substrates, (2) are transparent (or semi-transparent) electrodes, generally ITO films of ITO glass, and (3) are organic polymers The photoactive layer, (4) is the upper electrode of the aluminum film. Component (5) in Fig. 4 and Fig. 5 is an electron transport layer. The component (6) in Fig. 5 is a hole transport layer.

Detailed ways:

Embodiment 1, three-layer thin film structure organic photoelectric device

The structure of this optoelectronic device is shown in Figure 1. The implementation process is briefly described as follows: Conductive glass (ITO glass) is selected as the substrate (1), and the ITO film on it is used as the ^lower electrode (2). The metal phthalocyanine is thermally evaporated, and the photoactive layer (3) is prepared on the lower electrode (2). The method is to dissolve the ultra-large ring metal phthalocyanine into dimethyl ethylene oxide (DMSO) solution, spin-coat it on ITO glass, and then bake and dry it under the low vacuum condition that ordinary mechanical pumps can achieve to prepare the ultra-large ring metal phthalocyanine. A thin film photoactive layer (3), and finally an aluminum thin film upper electrode (4) is evaporated on the photoactive layer (3). This three-layer thin film structure is the same for electroluminescent devices, solar cells and photovoltaic devices.

Embodiment 2, four-layer thin film structure organic photoelectric device

The structure of this photoelectric device is shown in Figure 4. This device structure is based on the organic optoelectronic device with three-layer thin film structure as shown in Figure 1, and an electron transport layer is added between the supermacrocyclic metal phthalocyanine photoactive layer (3) and the aluminum thin film upper electrode (4) (5). The specific process is the same as that of the three-layer film structure organic photoelectric device in Example 1. The supermacrocyclic metal phthalocyanine photoactive layer (3) and the electron transport layer (5) can be prepared by thermal evaporation, and the supermacrocyclic metal phthalocyanine photoactive layer (5) can also be prepared by spin coating. Cyclic metal phthalocyanine photoactive layer (3) and electron transport layer (5). The material of the electron transport layer (5) can be selected from existing electron transport layer materials of organic polymer photoelectric devices. However, the electroluminescent device with four-layer thin film structure is different from the structure of solar cells and photovoltaic devices: the structure of the electroluminescent device is shown in Figure 4, and the electron transport layer (5) is located in the supermacrocyclic metal phthalocyanine light Between the active layer (3) and the upper electrode (4) of the aluminum film; and the electron transport layer (5) of the solar cell and photovoltaic device is located between the photoactive layer of super-macrocyclic metal phthalocyanine (3) and the lower electrode (2) of the ITO film .

Embodiment 3, organic optoelectronic device with five-layer thin film structure.

The structure of this optoelectronic device is shown in Figure 5. This device structure is based on the four-layer thin film structure organic photoelectric device shown in Figure 4, adding a layer of hole transport between the super-macrocyclic metal phthalocyanine photoactive layer (3) and the ITO thin film lower electrode (2) layer (6). The specific process is the same as the four-layer film structure organic photoelectric device of Example 2, and the supermacrocyclic metal phthalocyanine photoactive layer (3), electron transport layer (5) and hole transport layer (6) can be prepared by thermal evaporation, The supermacrocyclic metal phthalocyanine photoactive layer (3), electron transport layer (5) and hole transport layer (6) can also be prepared by spin coating. The materials of the electron transport layer (5) and the hole transport layer (6) can be selected from existing electron transport layer and hole transport layer materials of organic polymer photoelectric devices. The electroluminescent device of this five-layer film structure is also different from the structure of solar cells and photovoltaic devices: the structure of the electroluminescent device is shown in Figure 5, and the electron transport layer (5) is located in the photoactive layer of the super-large ring metal phthalocyanine (3) and the upper electrode (4) of the aluminum film, the hole transport layer (6) is positioned between the supermacrocyclic metal phthalocyanine photoactive layer (3) and the ITO thin film as the lower electrode (2); and the solar cell and photovoltaic The electron transport layer (5) of the device is located between the supermacrocyclic metallophthalocyanine photoactive layer (3) and the lower electrode (2) of the ITO film, and the hole transport layer (6) is located between the supermacrocyclic metallophthalocyanine photoactive layer (3) and the ITO film lower electrode (2). Between the electrodes (4) on the aluminum film.

The electron transport layer material described in the embodiments of the present invention, the hole transport layer material and the photoactive layer material used in the preparation of devices in the background technology can be "Semiconductor Laser Device Physics" (Jilin University Press, published in May 2002, Several representative materials listed on pages 294-296 of ISBN7-5601-2648-0/TN-10) are materials commonly used by persons of ordinary skill in the art in the process of preparing optoelectronic devices.

According to the accompanying drawings 6 and 7, the performance test of the ultra-macrocyclic metal phthalocyanine organic infrared photovoltaic device that we have developed shows that: this kind of device has good photovoltaic response characteristics in the wavelength range of 0.9 to 1.6 microns in the infrared region; The performance test of the ultra-macrocyclic metallophthalocyanine organic infrared light-emitting device developed by us shows that the device has good infrared light emission in the wavelength range of 1.5-1.6 microns, which is just the main wavelength band of optical fiber communication at present.

It can be seen from Examples 1 to 3 that the key process for preparing supermacrocyclic metallophthalocyanine organic infrared optoelectronic devices is the preparation of supermacrocyclic metallophthalocyanine photoactive layer (3), and the process conditions are: in a vacuum of 10 ^-4 Pa Next, use a quartz boat or a molybdenum boat to heat the supermacrocyclic metallophthalocyanine for thermal evaporation to prepare the photoactive layer (3). 3), the specific method is to dissolve the ultra-macrocyclic metal phthalocyanine in dimethyl ethylene oxide (DMSO) solution, spin-coat it on ITO glass, and then bake and dry it under the low vacuum condition that ordinary mechanical pumps can achieve to prepare ultra-large metal phthalocyanines. Cyclic metallophthalocyanine thin film photoactive layer (3).

Claims (6)

1. An organic infrared photoelectric device, consisting of a glass or flexible transparent substrate (1), a transparent or translucent thin film lower electrode (2), an organic polymer photoactive layer (3) and a metal thin film upper electrode (4), It is characterized in that: the organic polymer photoactive layer (3) is prepared from super macrocyclic metal phthalocyanine organic material. 2. organic infrared optoelectronic device as claimed in claim 1, is characterized in that: also have electron transport layer ( 5), thereby forming an organic light-emitting device with a four-layer thin film structure. 3. organic infrared optoelectronic device as claimed in claim 2, is characterized in that: also have hole transport layer ( 6), thereby forming an organic light-emitting device with a five-layer film structure. 4. organic infrared optoelectronic device as claimed in claim 1, is characterized in that: also have electron transport layer (5) between transparent or translucent thin film lower electrode (2) and super macrocyclic metal phthalocyanine photoactive layer (3) ), thus forming a four-layer thin-film organic photovoltaic device. 5. organic infrared optoelectronic device as claimed in claim 4, is characterized in that: also have hole transport layer ( 6), thereby forming an organic photovoltaic device with a five-layer thin film structure. 6. A method for preparing an organic infrared optoelectronic device as claimed in claim 1, the step is to successively vapor-deposit transparent or translucent film lower electrode (2), organic polymer photoactive layer (3) on the substrate (1) ) and a metal thin film upper electrode (4), characterized in that: the evaporation of the organic polymer photoactive layer (3) is carried out under the condition of a vacuum of 10 ^-4 Pa, using a quartz boat or a molybdenum boat to heat the ultra-large metal phthalocyanine material Thermal evaporation, thermal evaporation temperature is 600-900°C.

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