CN101834275B - Intermediate electrode layer used in inversed laminated organic solar cell and preparation method - Google Patents

Abstract

An intermediate electrode layer used in an inverted laminated organic solar cell and its preparation method. The electrode layer is deposited sequentially from bottom to top and includes: molybdenum trioxide layer, metal silver or gold or platinum layer, metal aluminum layer and metal calcium or magnesium layer. The method is: scrub the glass substrate coated with indium tin oxide with detergent, and then ultrasonically clean it with detergent, deionized water, acetone and alcohol in sequence; place the dried substrate in an ozone environment for plasma Processing, through the glove box, the substrate is transferred to a high vacuum chamber, 1 nanometer calcium metal is evaporated, the vacuum degree of the chamber is 9.0×10 ^-5 Pa, and then the substrate deposited with 1 nanometer calcium is transferred to the glove box In , the preparation of the conjugated polymer light-absorbing layer is carried out; the sample deposited with 1 nanometer calcium and the conjugated polymer light-absorbing layer with a set thickness is sent into a high vacuum chamber, and the molybdenum trioxide layer, metal silver or gold or Platinum layer, metallic aluminum layer and metallic calcium or magnesium layer. The invention can effectively protect the prepared lower light-absorbing layer.

Description

Intermediate electrode layer used in inverted tandem organic solar cells and preparation method

technical field

The invention relates to an intermediate electrode layer of an inverted laminated organic solar cell, in particular to an intermediate electrode layer used in an inverted laminated organic solar cell which uses a combination of a metal oxide layer and an ultra-thin multi-metal nanolayer structure film and Preparation.

Background technique

Solar energy is a green and renewable energy. Organic materials have certain unique advantages, such as low cost, portability, flexibility, and ease of mass production. This makes organic solar cells gradually become the most potential technology for converting sunlight energy into electricity. However, organic solar cells with conventional structures are limited by organic materials, such as narrow absorption range relative to the entire solar spectrum, short exciton diffusion distance, low mobility of charge carriers, and short lifetime. In order to overcome these drawbacks, stacked structures are applied to organic solar cells, which consist of two or more light-absorbing layers with complementary spectra as sub-cells. Therefore, being able to effectively connect the intermediate electrode layers of the subcells plays an extremely important role in the overall performance of the device.

Current intermediate electrode layers are mainly used in conventional tandem organic solar cells. The existing intermediate electrode layer is mainly prepared by vacuum evaporation method and liquid film-forming method. The combinations include: metallic silver nanoclusters, ultra-thin metallic gold, metallic aluminum/tungsten oxide, indium tin oxide/3,4 -Ethylenedioxythiophene doped polystyrene sulfonic acid, aluminum/gold/3,4-ethylenedioxythiophene doped polystyrene sulfonic acid, zinc oxide/3,4-ethylenedioxythiophene doped polystyrene sulfonic acid Styrenesulfonic acid, titanium oxide/3,4-vinyldioxythiophene doped polystyrenesulfonic acid, metallic aluminum/molybdenum trioxide, metallic aluminum/cesium-doped titanium oxide/3,4-vinyldioxy Thiophene doped polystyrene sulfonic acid. However, to date there is no intermediate electrode layer for inverted tandem organic solar cells. In addition to having high light transmittance and effectively connecting sub-cells, this intermediate electrode layer also needs to protect the prepared lower light-absorbing layer from being washed off.

Contents of the invention

The technical problem to be solved by the present invention is to provide an inverted laminate battery that can be applied to organic/conjugated polymer materials with different absorption spectrum ranges as the light-absorbing layer, which can effectively protect the prepared lower light-absorbing layer to An intermediate electrode layer used in an inverted stacked organic solar cell for realizing an inverted stacked organic solar cell and a preparation method thereof.

The technical solution adopted in the present invention is: an intermediate electrode layer used in an inverted stacked organic solar cell and a preparation method thereof, wherein the intermediate electrode layer used in an inverted stacked organic solar cell is arranged between the lower sub-cell and the Between the upper sub-batteries, from the lower sub-battery to the upper sub-battery are sequentially deposited: molybdenum trioxide layer, metal silver or gold or platinum layer, metal aluminum layer and metal calcium or magnesium layer, the molybdenum trioxide layer The thickness of the metal silver or gold or platinum layer is 0.5-1.5 nanometers, the thickness of the metal aluminum layer is 0.5-1.5 nanometers, and the thickness of the metal calcium or magnesium layer is 2.5-3.5 nanometers.

A method for preparing an intermediate electrode layer in an inverted stacked organic solar cell, comprising the steps of:

1) Selection and processing of the substrate:

First, the glass substrate coated with indium tin oxide was scrubbed with detergent, and then ultrasonically cleaned with detergent, deionized water, acetone and alcohol in sequence;

2) Preparation of substrate modification:

Place the dried substrate in an ozone environment for plasma treatment, then transfer the substrate to a high-vacuum chamber through a glove box, and vapor-deposit 1 nanometer calcium metal. The vacuum degree of the chamber is 9.0×10 ^{- 5} Pa, and then transfer the substrate deposited with 1 nanometer calcium to the glove box to prepare the conjugated polymer light-absorbing layer;

3) Preparation of the middle electrode layer:

The sample deposited with 1 nanometer calcium and a conjugated polymer light-absorbing layer with a set thickness is sent into a high vacuum chamber, and a molybdenum trioxide layer, a metal silver or gold or platinum layer, a metal aluminum layer and a metal calcium or magnesium layer are sequentially deposited .

The molybdenum trioxide layer, metal silver or gold or platinum layer, and metal calcium or magnesium layer described in step 3 are all deposited by thermal evaporation, and the metal aluminum layer is deposited by thermal evaporation or electron beam evaporation.

The deposition rate of the molybdenum trioxide layer described in step 3 is 0.02～0.05 nanometers/second, the deposition rate of the described metal silver or gold or platinum layer is 0.01～0.02 nanometers/second, the deposition rate of the described metal aluminum layer The deposition rate of the metal calcium or magnesium layer is 0.04-0.08 nm/s.

The intermediate electrode layer used in the inverted stacked organic solar cell and the preparation method of the present invention have the following characteristics.

1. Only a series of new combinations of metals and metal oxides are used to achieve the purpose of effectively connecting sub-cells. This scheme is easy to be used in various types of inverted tandem organic solar cells, thus guaranteeing the improvement of device performance. The preparation method and flow are simple and repeatable.

2. The optical characteristic of the present invention is high transmittance, which reduces the light loss caused by the multilayer structure. Its electrical characteristic is that it can effectively recombine the charge carrier pairs from the sub-batteries in this layer to achieve the purpose of the sum of the open circuit voltages of the corresponding inverted laminated batteries. Therefore, this invention is advantageous for use in inverted tandem organic solar cells with spectrally complementary light-absorbing layers as sub-cell components.

3. This invention can effectively protect the prepared lower light-absorbing layer to realize an inverted stacked organic solar cell.

Description of drawings

Fig. 1 is a structural representation of the present invention;

Fig. 2 is the optical transmittance spectrum of the intermediate electrode layer that the present invention obtains;

Fig. 3 is a comparison of the current density-voltage curves of two inverted sub-cells and an inverted stacked organic solar cell obtained in the present invention.

in:

1: Lower sub-battery 2: Molybdenum trioxide layer

3: Metal silver or gold or platinum layer 4: Metal aluminum layer

5: metal calcium or magnesium layer 6: upper sub-battery

7: Incident sunlight

Detailed ways

Specific examples are given below in conjunction with the accompanying drawings to further illustrate how to realize the intermediate electrode layer used in the inverted stacked organic solar cell and the preparation method of the present invention.

As shown in Figure 1, the intermediate electrode layer used in the inverted stacked organic solar cell of the present invention is arranged between the lower sub-cell 1 and the upper sub-cell 6, and is sequentially deposited from the lower sub-cell 1 to the upper sub-cell 6 The arrangement includes: molybdenum trioxide layer 2, metal silver or gold or platinum layer 3, metal aluminum layer 4 and metal calcium or magnesium layer 5.

The thickness of the molybdenum trioxide layer 2 is 7-8 nanometers, the thickness of the metal silver or gold or platinum layer 3 is 0.5-1.5 nanometers, the thickness of the metal aluminum layer 4 is 0.5-1.5 nanometers, and the metal calcium or magnesium layer 5 The thickness is 2.5-3.5 nanometers.

Select in the embodiment of the present invention: the thickness of molybdenum trioxide layer 2 is 7.5 nanometers, the thickness of metallic silver or gold or platinum layer 3 is 1 nanometer, the thickness of metallic aluminum layer 4 is 1 nanometer, the thickness of metallic calcium or magnesium layer 5 is 3 nanometers.

The preparation method for the intermediate electrode layer in the inverted laminated organic solar cell of the present invention comprises the following steps:

1) Selection and processing of the substrate:

First, the glass substrate coated with indium tin oxide was scrubbed with detergent, and then ultrasonically cleaned with detergent, deionized water, acetone and alcohol in sequence;

2) Preparation of substrate modification:

Place the dried substrate in an ozone environment for plasma treatment, then transfer the substrate to a high-vacuum chamber through a glove box, and vapor-deposit 1 nanometer calcium metal. The vacuum degree of the chamber is 9.0×10 ^{- 5} Pa, and then transfer the substrate deposited with 1 nanometer calcium to the glove box to prepare the conjugated polymer light-absorbing layer;

3) Preparation of the middle electrode layer:

Send the sample deposited with 1 nanometer calcium and a conjugated polymer light-absorbing layer with a set thickness into a high vacuum chamber, and sequentially deposit molybdenum trioxide layer 2, metal silver or gold or platinum layer 3, metal aluminum layer 4 and metal calcium or magnesium layer 5.

The thickness of the molybdenum trioxide layer 2 described in step 3 is 7-8 nanometers, the thickness of the metal silver or gold or platinum layer 3 is 0.5-1.5 nanometers, the thickness of the metal aluminum layer 4 is 0.5-1.5 nanometers, and the metal calcium or The thickness of the magnesium layer 5 is 2.5-3.5 nanometers.

Select in the embodiment of the present invention: the thickness of molybdenum trioxide layer 2 is 7.5 nanometers, the thickness of metallic silver or gold or platinum layer 3 is 1 nanometer, the thickness of metallic aluminum layer 4 is 1 nanometer, the thickness of metallic calcium or magnesium layer 5 is 3 nanometers.

The molybdenum trioxide layer 2, metal silver or gold or platinum layer 3 and metal calcium or magnesium layer 5 described in step 3 are all deposited by thermal evaporation, and the metal aluminum layer 4 is deposited by thermal evaporation or electron beam evaporation.

The deposition rate of the molybdenum trioxide layer 2 described in step 3 is 0.02-0.05 nanometers/second, the deposition rate of the described metal silver or gold or platinum layer 3 is 0.01-0.02 nanometers/second, and the deposition rate of the described metal aluminum layer 4 The deposition rate is 0.02-0.05 nanometers/second, and the deposition rate of the metal calcium or magnesium layer 5 is 0.04-0.08 nanometers/second.

Selected in the embodiment of the present invention: the deposition rate of molybdenum trioxide layer 2 is 0.05 nm/s, the deposition rate of metal silver or gold or platinum layer 3 is 0.01 nm/s, the deposition rate of metal aluminum layer 4 is 0.03 nm/s , the deposition rate of the metallic calcium or magnesium layer 5 is 0.06 nm/sec.

Figure 2 is the light transmittance spectrum of the intermediate electrode layer obtained in the present invention; Figure 3 is the comparison of the current density-voltage curves of the two inverted sub-cells and the inverted stacked organic solar cell obtained in the present invention.

Table 1 Performance comparison of two inverted sub-cells obtained in the present invention and an inverted stacked organic solar cell

Claims (4)

1. intermediate electrode layer that is used for the inverted stack organic solar batteries; Be arranged at down between straton battery (1) and the last straton battery (6), it is characterized in that, be provided with by what the following supreme straton battery of straton battery (1) (6) deposited successively: molybdenum trioxide layer (2); Argent or gold or platinum layer (3); Metal aluminium lamination (4) and calcium metal or magnesium layer (5), the thickness of described molybdenum trioxide layer (2) is 7～8 nanometers, the thickness of argent or gold or platinum layer (3) is 0.5～1.5 nanometer; The thickness of metal aluminium lamination (4) is 0.5～1.5 nanometer, and the thickness of calcium metal or magnesium layer (5) is 2.5～3.5 nanometers.

2. the described preparation method who is used for the intermediate electrode layer of inverted stack organic solar batteries of claim 1 is characterized in that, comprises the steps:

1) selection of substrate and processing:

The glass substrate that at first will be coated with tin indium oxide is cleaned with washing agent, uses washing agent, deionized water, acetone and alcohol ultrasonic cleaning subsequently successively again;

2) preparation of substrate modification:

With dried substrate, be put in and carry out Cement Composite Treated by Plasma in the ozone environment, through glove box, in the high vacuum chamber, the calcium metal of vapor deposition 1 nanometer, chamber vacuum degree are 9.0 * 10 with transfer substrates afterwards ^-5Pa, the substrate-transfer that will deposit 1 nanometer calcium is again carried out the preparation of conjugated polymer light-absorption layer in glove box;

3) preparation of intermediate electrode layer:

Send in the high vacuum chamber with the sample of the conjugated polymer light-absorption layer of setting thickness depositing 1 nanometer calcium, deposit molybdenum trioxide layer (2) successively, argent or gold or platinum layer (3), metal aluminium lamination (4) and calcium metal or magnesium layer (5).

3. the preparation method who is used for the intermediate electrode layer of inverted stack organic solar batteries according to claim 2; It is characterized in that; The described molybdenum trioxide layer of step 3 (2), argent or gold or platinum layer (3) and calcium metal or magnesium layer (5) all adopt the thermal evaporation vapor deposition, and described metal aluminium lamination (4) adopts thermal evaporation or electron beam evaporation plating.

4. the preparation method who is used for the intermediate electrode layer of inverted stack organic solar batteries according to claim 2; It is characterized in that; The deposition rate of the described molybdenum trioxide layer of step 3 (2) is 0.02～0.05 nm/sec; The deposition rate of described argent or gold or platinum layer (3) is 0.01～0.02 nm/sec, and the deposition rate of described metal aluminium lamination (4) is 0.02～0.05 nm/sec, and the deposition rate of described calcium metal or magnesium layer (5) is 0.04～0.08 nm/sec.

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