Patent Application
20140366947
The present disclosure relates to an optoelectronic field, more particularly relates to a polymer containing thiophene-benzene-thiophene unit, preparation method thereof and solar cell device using the polymer containing thiophene-benzene-thiophene unit.
Energy issues are the serious concern of all countries in the world. Solar energy is the best alternative energy for mankind in the future, how to convert solar energy into electrical power is a hotspot in research. In recent years, the popular conjugated polymer thin film organic solar cells have advantages of low cost, light weight, simple fabrication process, capable of being prepared into flexible devices, etc. In addition, many kinds of organic materials can be used as the material of the thin film organic solar cells, the thin film organic solar cells have great designability; it is promising to improve the performance of the organic solar cells through the design and optimization of materials.
In the polymer containing thiophene-benzene-thiophene unit, the thiophene is a typical electron-deficient unit, thus the polymer containing thiophene-benzene-thiophene unit has high hole mobility and shows an excellent photovoltaic performance. However, the band gap (the energy difference between the HOMO level and the LUMO level) of the conventional polymer containing thiophene-benzene-thiophene unit is relatively wide, which reduces the absorptivity to the photon in the solar spectrum; so that the power conversion efficiency of the solar cell having the polymer containing thiophene-benzene-thiophene unit is low.
Accordingly, it is necessary to provide a polymer containing thiophene-benzene-thiophene unit having high power conversion efficiency.
In addition, it is necessary to provide a method of preparing a polymer containing thiophene-benzene-thiophene unit.
In addition, it is necessary to provide a solar cell device having a polymer containing thiophene-benzene-thiophene unit.
A polymer containing thiophene-benzene-thiophene unit has a formula:
where R1 represents C1 to C20 alkyl, R2 represents C1 to C20 alkyl, n is an integer from 10 to 100.
A method of preparing a polymer containing thiophene-benzene-thiophene unit includes the steps of:
compounds A and B represented by the following formulas are provided:
where R1 represents C1 to C20 alkyl, R2 represents C1 to C20 alkyl; and
in an oxygen-free environment, the compound A and the compound B according to a molar ratio of 1:1 to 1:1.2 are added to an organic solvent containing a catalyst to perform a Suzuki coupling reaction; where the catalyst is organic palladium or a mixture of organic palladium and organic phosphine ligand; then the polymer containing thiophene-benzene-thiophene unit P is obtained:
where n is an integer from 10 to 100.
Preferably, the organic solvent is at least one selected from the group consisting of toluene, N,N-dimethylformamide, and tetrahydrofuran.
Preferably, the organic palladium is selected from the group consisting of bis(triphenylphosphine)palladium(II) dichloride, tetrakis(triphenylphosphine)palladium, and tris(dibenzylideneacetone)dipalladium; the organic phosphine ligand is selected from the group consisting of tri-tert-butylphosphine and 2-dicyclohexylphosphino-2′,6′-dimethoxybiphenyl; a molar ratio between the organic palladium and the organic phosphine ligand is 1:4 to 1:8.
Preferably, a molar ratio between the organic palladium in the catalyst and the compound A is 1:20 to 1:100.
Preferably, a reaction temperature of the Suzuki coupling reaction is 70° C. to 130° C., a reaction time is 12 to 96 hours.
Preferably, a reaction temperature of the Suzuki coupling reaction is 80° C. to 110° C.
Preferably, the method further includes purifying the polymer containing thiophene-benzene-thiophene unit P, where the step of purifying comprises the steps of:
methanol is added to a solution obtained by the Suzuki coupling reaction of the compound A and the compound B for precipitating and then filtering;
a solid obtained from the filtering is extracted with methanol and n-hexane successively;
the extracted solid is further extracted with chloroform; and
the chloroform solution is collected and the solvent is evaporated to obtain a purified polymer containing thiophene-benzene-thiophene unit P.
Preferably, a Soxhlet extractor is used for the extracting.
A solar cell device includes an active layer, where the active layer is made of a polymer containing thiophene-benzene-thiophene unit P having the following formula:
where R1 represents C1 to C20 alkyl, R2 represents C1 to C20 alkyl, n is an integer from 10 to 100.
In the polymer containing thiophene-benzene-thiophene unit, the thiophene-benzene-thiophene (TPT) derivative has characteristics of high hole mobility, narrow band gap, high absorption coefficient to the sunlight, and wide absorption range; and fluorene is a compound having the structure of rigid planar biphenyl, it has a high light stability and thermal stability and high hole mobility, thus when the polymer containing thiophene-benzene-thiophene unit and fluorene unit is applied to the solar cell device, the power conversion efficiency can be improved greatly.
A more detailed description of the polymer containing thiophene-benzene-thiophene unit and a preparation method thereof and an application thereof will be illustrated by reference to specific embodiments and drawings.
A polymer containing thiophene-benzene-thiophene unit of an embodiment has a formula:
where R1 represents C1 to C20 alkyl, R2 represents C1 to C20 alkyl, n is an integer from 10 to 100.
In the polymer containing thiophene-benzene-thiophene unit, the thiophene-benzene-thiophene (TPT) derivative has characteristics of high hole mobility, narrow band gap, high absorption coefficient to the sunlight, and wide absorption range; and fluorene is a compound having the structure of rigid planar biphenyl, it has high light stability and thermal stability and high hole mobility, thus when the polymer containing thiophene-benzene-thiophene unit and fluorene is applied to the solar cell device, the power conversion efficiency can be greatly improved.
Referring to
Step S1, compounds A and B are provided.
The formula of the compound A is
where R1 represents C1 to C20 alkyl.
The formula of the compound B is
where R2 represents C1 to C20 alkyl.
In the illustrated embodiment, the compound A can be synthesized according to the method disclosed in the reference of Macromolecule, 2008,41,5519 or purchased from the market. The compound B can be purchased from the market.
Step S2, the polymer containing thiophene-benzene-thiophene unit P is prepared.
In an oxygen-free environment, the compound A and the compound B according to a molar ratio of 1:1 to 1:1.2 are added to an organic solvent containing a catalyst to perform a Suzuki coupling reaction. The catalyst is organic palladium or a mixture of organic palladium and organic phosphine ligand, then the polymer containing thiophene-benzene-thiophene unit P is obtained:
where R1 represents C1 to C20 alkyl, R2 represents C1 to C20 alkyl, n is an integer from 10 to 100.
In the illustrated embodiment, the organic solvent is at least one selected from the group consisting of toluene, N,N-dimethylformamide, and tetrahydrofuran. It should be understood that the organic solution can also be other solvents, as long as it can dissolve the compound A and compound B.
In the illustrated embodiment, the organic palladium is selected from the group consisting of bis(triphenylphosphine)palladium(II) dichloride, tetrakis(triphenylphosphine)palladium, and tris(dibenzylideneacetone)dipalladium. The organic phosphine ligand is selected from the group consisting of tri-tert-butylphosphine and 2-dicyclohexylphosphino-2′,6′-dimethoxybiphenyl. A molar ratio between the organic palladium and the organic phosphine ligand in the mixture of the organic palladium and the organic phosphine ligand is 1:4 to 1:8. Preferably, the catalyst is a mixture of tris(dibenzylideneacetone)dipalladium and tri-tert-butylphosphine. It should be understood that the organic palladium and the organic phosphine ligand are not limited to the types as listed, as long as the compound A and compound B can perform the Suzuki coupling reaction catalyzed by the catalyst.
In the illustrated embodiment, a molar ratio between the organic palladium in the catalyst and the compound A is 1:20 to 1:100. It should be understood that the molar ratio between the organic palladium and the compound A is not limited to 1:20 to 1:100, as long as a catalytic amount of the catalyst is added to the organic solvent of the compound A and compound B.
In the illustrated embodiment, a reaction temperature of the Suzuki coupling reaction is 70° C. to 130° C., a reaction time is 12 to 96 hours. Preferably, the reaction temperature of the Suzuki coupling reaction is 80° C. to 110° C., the reaction time is 24 to 72 hours. It should be understood that the reaction temperature is not limited to 70° C. to 130° C., as long as the compound A and compound B can react; the reaction time is not limited to 12 to 96 hours, as long as the reaction of compound A and compound B is completed.
Step S3, the polymer containing thiophene-benzene-thiophene unit P is purified.
Methanol is added to a reaction solution obtained by the Suzuki coupling reaction of the compound A and the compound B for precipitating and then the solution is filtered. A solid obtained from the filtering is extracted with methanol and n-hexane successively, then the solid is further extracted with chloroform; and the chloroform solution is collected and the solvent is evaporated to obtain a purified polymer containing thiophene-benzene-thiophene unit P.
In the illustrated embodiment, a Soxhlet extractor is used for the extracting.
In the illustrated embodiment, after the chloroform solution is collected and the solvent is evaporated, the obtained purified polymer containing thiophene-benzene-thiophene unit P is dried at a temperature of 50° C. for 24 hours.
The synthetic route of the method of preparing the polymer containing thiophene-benzene-thiophene unit is relatively simple, the manufacturing cost is reduced. The prepared polymer containing thiophene-benzene-thiophene unit has high hole mobility and narrow band gap.
The specific examples are shown as follows.
This example disclosed a poly{bis(4,4-bis(4-n-octyl-phenyl)-indeno[1,2-b]thiophene)-co-9,9-di-n-octyl fluorene} (polymer containing thiophene-benzene-thiophene unit P1) with the following formula:
The preparation process of the polymer containing thiophene-benzene-thiophene unit P1 was shown as follow:
Under the protection of nitrogen, bis(2-bromo-4,4-bis(4-n-octyl-phenyl)-indeno[1,2-b]thiophene (353 mg, 0.3 mmol), 2,2′-(9,9-dioctyl-9H-fluorene-2,7-diyl)bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolane) (193 mg, 0.3 mmol), tris(dibenzylideneacetone)dipalladium (13.75 mg, 0.015 mmol), and tri-tert-butylphosphine (24.2 mg, 0.12 mmol) were dissolved in 12ml of toluene, and a potassium carbonate solution (3 mL, 2 mol/L) was added to the solution, then nitrogen was sufficiently introduced to exhaust the air for approximately 30 minutes, the reaction lasted for 48 hours at a temperature of 95° C. in the condition of stirring. The polymerization reaction stopped after cooling. 40 mL of methanol was added to flask, the reaction solution was precipitated to obtain sediment. The sediment was extracted with methanol and n-hexane successively for 24 hours by a Soxhlet extractor after filtering. The sediment was then extracted by using chloroform as a solvent until the reaction solution was colorless. A chloroform solution was collected and rotary evaporated to obtain a red powder, and finally the red powder was dried under vacuum at a temperature of 50° C. for 24 hours to obtain a product with a yield of 72%.
The reaction of the prepared polymer containing thiophene-benzene-thiophene unit P1 was shown as follows:
Test results of molecular weight were: Molecular weight (GPC, THF, R.I): Mn=74.2 kDa, Mw/Mn=2.2.
Referring to
This example disclosed a poly{bis(4,4-bis(4-methylphenyl)-indeno[1,2-b]thiophene-co-9,9-di(n-eicosyl)fluorene} (polymer containing thiophene-benzene-thiophene unit P2) with the following formula:
The preparation process of the polymer containing thiophene-benzene-thiophene unit P2 was shown as follow:
Under the protection of nitrogen, bis(2-bromo-4,4-bis(4-methylphenyl)-indeno[1,2-b]thiophene) (157 mg, 0.2 mmol), 2,2′-9,9-di(n-eicosyl)fluorene-2,7-diyl)bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolane) (176 mg, 0.22 mmol), and 15 ml of N,N-dimethylformamide were added to a flask, and a potassium carbonate solution (2 mL, 2 mol/L) was added to the solution; then the flask was evacuated to remove the oxygen and the nitrogen was introduced sufficiently to the flask, then bis(triphenylphosphine)palladium(II) dichloride (5.6 mg,0.008 mmol) was added, the solution was heated to 120° C. to react for 36 hours; the mixed solution was dropped to 50 ml of methanol for precipitation after cooling to room temperature. Sediment was obtained; the sediment was extracted with methanol and n-hexane successively for 24 hours by a Soxhlet extractor after filtering. The sediment was then extracted by using chloroform as a solvent until the reaction solution was colorless. A chloroform solution was collected and rotary evaporated to obtain a red powder, and finally the red powder was filtrated under vacuum for overnight to obtain a product with a yield of 63%.
The reaction of the prepared polymer containing thiophene-benzene-thiophene unit P2 was shown as follows:
Test results of molecular weight were: Molecular weight (GPC, THF, R.I): Mn=58.1 kDa, Mw/Mn=2.3.
The poly{bis(4,4-bis(4-methylphenyl)-indeno[1,2-b]thiophene-co-9,9-di(n-eicosyl)fluorene} of Example 2 was tested by UV-visible absorption spectra. The results shown that the conjugated polymer had a wide absorption between 400-750 nm, the maximum absorption peak was at about 628 nm.
This example disclosed a poly{bis(4,4-bis(4-n-eicosyl alkylphenyl)-indeno[1,2-b]thiophene-co-9,9-dimethyl-fluorene} (polymer containing thiophene-benzene-thiophene unit P3) with the following formula:
The preparation process of the polymer containing thiophene-benzene-thiophene unit P3 was shown as follow:
Under the protection of nitrogen, bis(2-bromo-4,4-bis(4-n-eicosyl alkylphenyl)-indeno[1,2-b]thiophene) (555 mg, 0.3 mmol), 2,2′-(9,9-dimethyl-fluorene-2,7-diyl)bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolane) (134 mg, 0.36 mmol), and 15 ml of tetrahydrofuran were added to a 50 mL of 2-necked flask, respectively; nitrogen was sufficiently introduced to exhaust the air for approximately 20 minutes; then tetrakis(triphenylphosphine)palladium (4 mg, 0.003 mmol) was added, and a potassium carbonate solution (3 mL, 2 mol/L) was added to the solution, then nitrogen was introduced sufficiently to exhaust the air for approximately 10 minutes, the reaction lasted for 96 hours at a temperature of 70° C. in the condition of stirring. The polymerization reaction stopped after cooling. 40 mL of methanol was added to the flask, the reaction solution was precipitated to obtain sediment; the sediment was extracted with methanol and n-hexane successively for 24 hours by a Soxhlet extractor after filtering. The sediment was then extracted by using chloroform as a solvent until the reaction solution was colorless. A chloroform solution was collected and rotary evaporated to obtain a red powder, and finally the red powder was dried under vacuum at a temperature of 50° C. for 24 hours to obtain a product with a yield of 87%.
The reaction of the prepared polymer containing thiophene-benzene-thiophene unit P3 was shown as follows:
Test results of molecular weight were: Molecular weight (GPC, THF, R.I): Nn=87.8 kDa, Mw/Mn=2.1.
The poly{bis(4,4-bis(4-n-eicosyl alkylphenyl)-indeno[1,2-b]thiophene-co-9,9-dimethyl-fluorene} of Example 3 was tested by UV-visible absorption spectra. The results shown that the conjugated polymer had a wide absorption between 400-750 nm, the maximum absorption peak was at about 626 nm.
This example disclosed a poly{bis(4,4-bis(4-n-hexyl-phenyl)-indeno[1,2-b]thiophene-co-9,9-bis(n-dodecyl)fluorene} (polymer containing thiophene-benzene-thiophene unit P4) with the following formula:
The preparation process of the polymer containing thiophene-benzene-thiophene unit P4 was shown as follow:
Under the protection of nitrogen, bis(2-bromo-4,4-bis(4-n-hexyl-phenyl)-indeno[1,2-b]thiophene) (213 mg, 0.2 mmol), 2,2′-(9,9-n-eicosyl-fluorene-2,7-diyl)bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolane) (181 mg, 0.24 mmol), and 15 ml of N,N-dimethylformamide were added to a flask; and a potassium carbonate solution (2 mL, 2 mol/L) was added to the solution; then the flask was evacuated to remove the oxygen and the nitrogen was introduced, then bis(triphenylphosphine)palladium(II) dichloride (7.2 mg, 0.01 mmol) was added, the solution was heated to 130° C. to react for 24 hours. The mixed solution was dropped to 50 ml of methanol for precipitation after cooling to room temperature. Sediment was obtained; the sediment was extracted with methanol and n-hexane successively for 24 hours by a Soxhlet extractor after filtering. The sediment was then extracted by using chloroform as a solvent until the reaction solution was colorless. A chloroform solution was collected and rotary evaporated to obtain a red powder, and finally the red powder was filtrated under vacuum for overnight to obtain a product with a yield of 68%.
The reaction of the prepared polymer containing thiophene-benzene-thiophene unit P4 was shown as follows:
Test results of molecular weight were: Molecular weight (GPC, THF, R.I): Mn=51.0 kDa, Mw/Mn=2.3.
The poly{bis(4,4-bis(4-n-hexyl-phenyl)-indeno[1,2-b]thiophene-co-9,9-bis(n-dodecyl)fluorene} of Example 4 was tested by UV-visible absorption spectra. The results shown that the conjugated polymer has a wide absorption between 400-750 nm, the maximum absorption peak was at about 622 nm.
Referring to
In the illustrated embodiment, the substrate 51 is made of glass.
The anode 52 is formed on a side of the substrate 51. In the illustrated embodiment, the anode 52 is made of ITO (indium tin oxide). Preferably, the ITO has a sheet resistance of 10 to 20 Ω/sq.
The buffer layer 53 is formed on a side of the anode 52 away from the substrate 51. The buffer layer 53 is made of a composite of poly 3,4-ethylenedioxythiophene and poly styrene sulfonate (PEDOT: PSS).
The active layer 54 is formed on a side of the buffer layer 53 away from the anode 52. The active layer 54 includes an electron donor material and an electron acceptor material. A molar ratio of the electron donor material and the electron acceptor material is 1:2. The electron acceptor material can be (6,6)-phenyl-C61-butyric acid methyl ester (PCBM). The electron donor material is the polymer containing thiophene-benzene-thiophene unit P. In the illustrated embodiment, the electron donor material is poly{bis(4,4-bis(4-n-octyl-phenyl)-indeno[1,2-b]thiophene)-co-9,9-di-n-octyl fluorene} obtained from the example 1.
The cathode 55 is formed on a side of the active layer 54 away from the buffer layer 53. The cathode 55 can be an aluminum electrode or a double-layer metal electrode, such as Ca/Al or Ba/Al and so on; the thickness of the cathode 55 is preferably 150 nm, 35 nm, 120 mm, or 70 nm. In the illustrated embodiment, the cathode 55 is made of aluminum, and the thickness of the cathode 55 is 150 nm.
It can be understood that, the buffer layer 53 can be omitted, and then the active layer 54 is formed directly on the surface of the anode 52.
The manufacturing processes of the solar cell device 50 were shown as follows:
The anode 52 was formed on a side of the substrate 51; then cleaned by ultrasonic and treated with an oxygen-Plasma; then the anode 52 was coated with a layer of PEDOT: PSS for modification to form the buffer layer 53.
The active layer 54 was coated on the buffer layer 53. The active layer 54 included an electron donor material and an electron acceptor material. The electron acceptor material was PCBM. The electron donor material was the poly{bis(4,4-bis(4-n-octyl-phenyl)-indeno[1,2-b]thiophene)-co-9,9-di-n-octyl fluorene} obtained from the example 1.
The cathode 55 was deposited on the active layer 54. In the illustrated embodiment, the cathode 55 was an aluminum layer formed by vacuum deposition. The thickness of the cathode 55 was 150 nm.
In the illustrated embodiment, the solar cell device 50 was heated at 110° C. for 4 hours in a sealed condition, and then cooled to room temperature. The anneal of the solar cell device can effectively increase the arranged orderliness and regularity of each group in the molecule and the molecular chain segments, and the carrier mobility and the efficiency of the transmission speed were improved, thereby improving the photoelectric conversion efficiency.
Under the AM1.5G100 mW/cm2 illumination, the power conversion efficiency of the bulk-heterojunction solar cell device 50 using the polymer of example 1 as the electron donor material is 4.5%,
When the solar cell device 50 is in use, under illumination, the light is transmitted through the substrate 51 and the anode 52, then the light energy is absorbed by the hole-conduction type electroluminescent material of the active layer 54, thus generating excitons. The excitons migrate to the interface between the electron donor and acceptor materials, and the electrons are transferred to the electron acceptor material, such as PCBM, the charges are separated, thereby forming the free carriers, i.e. the free electrons and the holes. The free electrons are transferred to the cathode 55 along the electron acceptor material and collected by the cathode; the free holes are transferred to the anode 52 along the electron donor material and collected by the anode 52, thereby forming the photocurrent and photovoltage, and photoelectric conversion is implemented. When a load is connected, the device is capable of supplying power. Since the hole-conduction type electroluminescent material has a wide spectral response range, the light energy is fully utilized to gain much higher photoelectric conversion efficiency, and the power generation capacity of the organic solar cell is increased. Moreover, this type organic material is also capable of reducing the weight of the organic solar cell; and it can be made by spin-coating and other technologies for mass production.
Although the present invention has been described with reference to the embodiments thereof and the best modes for carrying out the present invention, it is apparent to those skilled in the art that a variety of modifications and changes may be made without departing from the scope of the present invention, which is intended to be defined by the appended claims.
| Filing Document | Filing Date | Country | Kind | 371c Date |
|---|---|---|---|---|
| PCT/CN2012/072216 | 3/12/2012 | WO | 00 | 7/1/2014 |
