KR20160141541A - Hole transfer material, method for preparation thereof, and solar cell comprising the same - Google Patents
Hole transfer material, method for preparation thereof, and solar cell comprising the same Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 13
- 239000000463 material Substances 0.000 title abstract description 14
- 238000002360 preparation method Methods 0.000 title description 2
- 238000012546 transfer Methods 0.000 title description 2
- 230000005525 hole transport Effects 0.000 claims abstract description 13
- 239000000126 substance Substances 0.000 claims abstract description 8
- 125000000956 methoxy group Chemical class [H]C([H])([H])O* 0.000 claims abstract description 6
- 150000001875 compounds Chemical class 0.000 claims description 43
- 238000006243 chemical reaction Methods 0.000 claims description 10
- CYPYTURSJDMMMP-WVCUSYJESA-N (1e,4e)-1,5-diphenylpenta-1,4-dien-3-one;palladium Chemical compound [Pd].[Pd].C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1 CYPYTURSJDMMMP-WVCUSYJESA-N 0.000 claims description 6
- 125000003545 alkoxy group Chemical group 0.000 claims description 6
- BWHDROKFUHTORW-UHFFFAOYSA-N tritert-butylphosphane Chemical compound CC(C)(C)P(C(C)(C)C)C(C)(C)C BWHDROKFUHTORW-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 4
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 claims description 4
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- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims description 2
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 claims description 2
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 abstract description 13
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- 239000011368 organic material Substances 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
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- 238000004770 highest occupied molecular orbital Methods 0.000 description 3
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- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
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- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
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- 239000013078 crystal Substances 0.000 description 2
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- 239000007788 liquid Substances 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 238000013086 organic photovoltaic Methods 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
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- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 229910001887 tin oxide Inorganic materials 0.000 description 2
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 2
- OLRBYEHWZZSYQQ-VVDZMTNVSA-N (e)-4-hydroxypent-3-en-2-one;propan-2-ol;titanium Chemical compound [Ti].CC(C)O.CC(C)O.C\C(O)=C/C(C)=O.C\C(O)=C/C(C)=O OLRBYEHWZZSYQQ-VVDZMTNVSA-N 0.000 description 1
- 0 *c1ccccc1N(c(cc1)cc(C(c2c3)(c4c5)c6cc(N(c7ccccc7*)c(cccc7)c7I)ccc6-c4ccc5N(c4ccccc4*)c4ccccc4*)c1-c2ccc3N(c1c(*)cccc1)c1ccccc1*)c1c(*)cccc1 Chemical compound *c1ccccc1N(c(cc1)cc(C(c2c3)(c4c5)c6cc(N(c7ccccc7*)c(cccc7)c7I)ccc6-c4ccc5N(c4ccccc4*)c4ccccc4*)c1-c2ccc3N(c1c(*)cccc1)c1ccccc1*)c1c(*)cccc1 0.000 description 1
- OUPAROZONRLKSV-UHFFFAOYSA-N 2-methoxy-n-(2-methoxyphenyl)aniline Chemical compound COC1=CC=CC=C1NC1=CC=CC=C1OC OUPAROZONRLKSV-UHFFFAOYSA-N 0.000 description 1
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- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- QXKHYNVANLEOEG-UHFFFAOYSA-N Methoxsalen Chemical group C1=CC(=O)OC2=C1C=C1C=COC1=C2OC QXKHYNVANLEOEG-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
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- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 description 1
- 239000011245 gel electrolyte Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 229940071870 hydroiodic acid Drugs 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 230000000873 masking effect Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
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- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C211/00—Compounds containing amino groups bound to a carbon skeleton
- C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
- C07C211/54—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to two or three six-membered aromatic rings
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C13/00—Cyclic hydrocarbons containing rings other than, or in addition to, six-membered aromatic rings
- C07C13/28—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof
- C07C13/32—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings
- C07C13/54—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings with three condensed rings
- C07C13/547—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings with three condensed rings at least one ring not being six-membered, the other rings being at the most six-membered
- C07C13/567—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings with three condensed rings at least one ring not being six-membered, the other rings being at the most six-membered with a fluorene or hydrogenated fluorene ring system
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C13/00—Cyclic hydrocarbons containing rings other than, or in addition to, six-membered aromatic rings
- C07C13/28—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof
- C07C13/32—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings
- C07C13/72—Spiro hydrocarbons
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- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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- Y02E10/50—Photovoltaic [PV] energy
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Abstract
Description
The present invention relates to a hole transport material, a method of manufacturing the same, and a solar cell including the same.
Researches on renewable and clean alternative energy sources such as solar energy, wind power, and hydro power are actively being conducted to solve the global environmental problems caused by the depletion of fossil energy and its use.
Of these, there is a great interest in solar cells that change electrical energy directly from sunlight. The term "solar cell" as used herein refers to a cell that generates a current-voltage by utilizing a photovoltaic effect that absorbs light energy from sunlight to generate electrons and holes.
Currently, np diode-type silicon (Si) single crystal based solar cells with a light energy conversion efficiency of more than 20% can be manufactured and used for actual solar power generation. Compound semiconductors such as gallium arsenide (GaAs) There is also solar cell using. However, since such an inorganic semiconductor-based solar cell requires a highly refined material for high efficiency, a large amount of energy is consumed for refining the raw material, and expensive process equipment is required in the process of making single crystal or thin film using raw material And the manufacturing cost of the solar cell can not be reduced.
Accordingly, in order to manufacture a solar cell at a low cost, it is necessary to drastically reduce the cost of the core material or the manufacturing process of the solar cell. As an alternative to the inorganic semiconductor-based solar cell, a dye- Solar cells are being actively studied.
Dye-sensitized solar cell (DSSC) was first developed by Professor Michael Gratzel of the Lausanne University of Technology in Switzerland (1991) and introduced to Nature magazine (Vol. 353, p. 737) .
In the early dye-sensitized solar cell structure, a dye that absorbs light is adsorbed on a porous photo-electrode on a transparent electrode film through which light and electricity pass, and then another conductive glass substrate is placed on top and a simple structure . The working principle of a dye-sensitized solar cell is as follows. When dye molecules chemically adsorbed on the surface of a porous photocathode absorb solar light, dye molecules generate electron-hole pairs, and electrons are converted into conduction tines of semiconductor oxide used as a porous photocathode Injected and transferred to the transparent conductive film to generate a current. The holes remaining in the dye molecules are transferred to the photocathode by the hole conduction or hole conductive polymer by the oxidation-reduction reaction of the liquid or solid electrolyte, and form a complete solar cell circuit, .
In this dye-sensitized solar cell structure, the transparent conductive film is mainly composed of fluorine doped tin oxide (FTO) or indium doped tin oxide (ITO), and a nanotube having a wide band gap is used as the porous photo cathode. The dyestuff is particularly well absorbed and has a lowest unoccupied molecular orbital (LUMO) energy level of the dye than the energy level of the condiction band of the photocathode material, which facilitates the separation of the exciton produced by the light, Various materials are chemically synthesized and used. The highest efficiency of liquid dye-sensitized solar cells reported so far is 11-12% for about 20 years. Although the efficiency of the liquid dye-sensitized solar cell is relatively high, it is likely to be commercialized. However, there is a problem in terms of stability with time due to volatile liquid electrolyte and low cost due to use of expensive ruthenium (Ru) dye.
In order to solve this problem, a nonvolatile electrolyte using an ionic solvent, a polymer gel electrolyte, and a pure organic dyestuff have been studied in place of a volatile liquid electrolyte, but a dye sensitized with a volatile liquid electrolyte and a ruthenium dye There is a problem that the efficiency is lower than that of the solar cell.
Organic photovoltaics (OPVs), which have been studied extensively since mid-1990, have been used to study organic materials with electron donor (D or often called hole acceptor) characteristics and electron acceptor (A) . When a solar cell made of organic molecules absorbs light, electrons and holes are formed. This is called an exiton. The exciton moves to the DA interface to separate the charge, the electrons move to the electron acceptor, and the hole moves to the electron donor, generating a photocurrent.
Since the distance that the exciton generated from the electron donor can travel normally is very short, about 10 nm, the photoconductivity can not be accumulated thickly, and the efficiency of the photoconductivity is low due to low light absorption. In recent years, however, efficiency has greatly increased with the introduction of the so-called bulk heterojunction (BHJ) concept of increasing the surface area at the interface and the development of donor organic materials having a small band gap that is easy to absorb a wide range of solar light, Organic solar cells with efficiency over 8% have been reported (Advanced Materials, 23 (2011) 4636).
Organic solar cells are easier to fabricate than existing solar cells because of their easy processability and diversity of organic materials and low unit cost. Therefore, it is possible to realize low cost manufacturing cost compared to existing solar cells. However, in the organic solar cell, the structure of the BHJ is deteriorated by moisture or oxygen in the air and the efficiency thereof is rapidly lowered, that is, there is a serious problem in the stability of the solar cell. As a method to solve this problem, it is possible to increase the stability by introducing the full sealing technology, but there is a problem that the price is increased.
As a method for solving the problems of the dye-sensitized solar cell by the liquid electrolyte, Prof. Mikael Gratzel of the Department of Chemistry, Lausanne University of Technology, Switzerland, inventor of the dye-sensitized solar cell, proposed a solid-type hole conductive organic material Spiro-OMeTAD (N, N-di-p-methoxyphenylamine) -9,9'-spirobifluorine) was used as a dye-sensitized solar cell with an efficiency of 0.74%.
Thereafter, research on increasing the power generation efficiency of the solar cell by modifying the chemical structure of the Spiro-OMeTAD has been progressing. Recently, as a part of the methoxy group of Spiro-OMeTAD, ortho- (J. Am. Chem. Soc., 2014, 136 (22), pp. 7837-7840). Nevertheless, a method for increasing the efficiency of the solar cell is still required.
Accordingly, the inventors of the present invention studied compounds capable of enhancing the efficiency of solar cells as compared with Spiro-OMeTAD, and thus the compounds described below can remarkably increase the efficiency of solar cells compared with Spiro-OMeTAD derivatives reported so far To complete the present invention.
The present invention is to provide Spiro-OMeTAD derivatives of novel structure and a process for their preparation.
The present invention also provides a composition for hole transport comprising the compound. The present invention also provides a solar cell comprising the above compound.
In order to solve the above problems, the present invention provides a compound represented by the following formula (1): < EMI ID =
[Chemical Formula 1]
In Formula 1,
R 1 and R 2 are each independently C 1 -4 alkoxy.
The compound represented by the above formula (1), eight C 1 -4 alkoxy (methoxy), unlike the structure of the Spiro-OMeTAD release conventionally used has a characteristic that is substituted at the ortho (ortho) of the phenyl. The C 1 -4 alkoxy (methoxy) substituted in the orthosus induces distortion of the overall chemical structure of
Therefore, when the compound of Formula 1 is used as a hole transporting layer of a solar cell, the electron blocking effect is enhanced by the increased LUMO energy level, so that the series resistance of the solar cell is decreased and the parallel resistance is increased, It is possible to remarkably improve the performance index and the power generation efficiency.
Preferably, R 1 and R 2 are the same as each other.
Also preferably, R 1 and R 2 are methoxy.
The present invention also relates to a process for preparing a compound represented by the general formula (1), which comprises reacting a compound represented by the following general formula (2) and a compound represented by the following general formula (3) A method for producing the compound is provided.
[Reaction Scheme 1]
In the
The molar ratio of the compound represented by Formula 2 and the compound represented by Formula 3 is preferably 1: 4 to 6. The molar ratio is preferably 1: 4 or more, and when the molar ratio is more than 1: 6, the reaction efficiency does not substantially increase.
Also, for the efficiency of the reaction, 1) sodium tert-butoxide or potassium tert-butoxide; 2) tris (dibenzylideneacetone) dipalladium (0) or palladium acetate (Pd (OAc) 2 ); And 3) tri-tert-butylphosphine. The amount of the substance to be used is preferably 6 to 10 mol, 0.05 to 0.2 mol, and 0.1 to 0.4 mol, respectively, based on 1 mol of the compound represented by the formula (2).
Also, the reaction is preferably carried out at 80 to 150 ° C.
After this reaction, purification steps commonly used in the art can be added.
Also, the present invention provides a composition for oral delivery comprising the compound represented by the above formula (1). The present invention also provides a solar cell comprising the compound represented by Formula 1.
As described above, the compound represented by Formula 1 has a high LUMO energy level, and thus can be usefully used as an electron transferring material. In addition, when used as a hole-transporting material for a solar cell, the performance index of the solar cell can be remarkably improved.
The solar cell according to the present invention may have a structure commonly used in the art, except that the compound represented by Formula 1 is used as a hole-transporting material.
According to one embodiment of the present invention, when the compound represented by Formula 1 according to the present invention is used as a hole transporting material instead of Spiro-OMeTAD, the efficiency of the solar cell is remarkably improved.
The compounds according to the present invention, has a higher LUMO energy level ortho by the steric effect of a C 1 -4 alkoxy which is substituted with a, so that if used as a major transfer layer of a solar cell to significantly increase the performance index of the solar cell Can be.
1 shows the 1 H-NMR results of the compounds prepared in the examples of the present invention.
FIG. 2 shows the short-circuit current density-open-circuit voltage curve of a solar cell using the compound prepared in Examples and Comparative Examples of the present invention as a hole transport layer.
Best Mode for Carrying Out the Invention Hereinafter, preferred embodiments are shown to facilitate understanding of the present invention. However, the following examples are intended to illustrate the present invention without limiting it thereto.
Example
In a 50 mL flask, 2,2'-dimethoxydiphenylamine (2.00 g, 8.72 mmol), 2,2 ', 7,7'-tetrabromo-9,9'-spiro [9H-fluorene] Butoxide (1.12 g, 1.12 g, 11.6 mmol), tris (dibenzylideneacetone) dipalladium (0) (0.071 g, 0.078 mmol) and tri-tert- butylphosphine (0.025 g, 0.12 mmol) were mixed. 15 mL of anhydrous toluene was added to the flask under a nitrogen atmosphere. The reaction mixture was heated to 110 < 0 > C under reflux for 12 hours under a nitrogen atmosphere. The mixture was cooled to room temperature, extracted with ethyl acetate and brine, dried over anhydrous MgSO 4 , hot filtered with ethanol, and washed with acetone to obtain 1.18 g of the title compound. 1 H-NMR of the compound thus obtained is shown in Fig.
Comparative Example One
Compounds of the above structure were prepared according to the literature (J. Am. Chem. Soc., 2014, 136 (22), pp 7837-7840).
Comparative Example 2
Compounds of the above structure were prepared according to the literature (J. Am. Chem. Soc., 2014, 136 (22), pp 7837-7840).
Experimental Example One: HOMO / LUMO Calculation of
HOMO and LUMO of the compounds of the above Examples and Comparative Examples 1 and 2 were theoretically calculated. All calculations were performed with the Gaussian 09 program package (Gaussian 09, revision C.01, Gaussian, Inc., Wallingford CT, 2010). The structure optimization was performed using PBE function (Phys. Rev. Lett., 1997, 78, 1396) and TDDFT electronic excitation calculation using PBE0 functional (J. The calculated results are shown in Table 1 below.
As shown in the above Table 1, the LUMO of the Examples is higher than that of Comparative Examples 1 and 2, which is due to the lower resonance stabilization because the 8 methoxy groups in the compounds of the Examples are substituted by ortho of phenyl do.
Experimental Example 2: Manufacturing and performance evaluation of solar cell
Step 1) Manufacture of solar cell
TiO 2 (bl-TiO 2 ), a 60 nm thick barrier layer, was blocked with 20 mM titanium diisopropoxide bis (acetylacetonate) at 450 ° C. to block direct contact between the FTO and the hole transport layer by spraying heat deposited F-doped SnO 2 (FTO, Pilkington, TEC8) it is deposited onto a substrate. TiO 2 particles having a diameter of about 40 nm were prepared by hydrothermally treating the amorphous TiO 2 solution with colloidization from titanium isopropoxide (Aldrich, 98%) at 250 ° C. for 12 hours, and finally, TiO 2 paste . The above paste was spin-coated on a bl-TiO 2 / FTO substrate to form a 250 nm thick porous TiO 2 (mp-TiO 2 ) film. The film was sintered at 500 ° C. for 1 hour, Respectively.
30 mL was reacted with hydroiodic acid (57% in water, Aldrich) with 27.86 mL of methylamine was stirred for 2 hours at 0 ℃ in (40% in methanol, Junsei Chemical Co., Ltd.) and 250 mL flask, CH 3 NH 3 < / RTI > The solvent was evaporated at 50 < 0 > C for 1 hour to recover the precipitate. The recovered precipitate was dissolved in ethanol, recrystallized with diethyl ether, and then dried in a vacuum oven at 60 DEG C for 24 hours. The synthesized CH 3 NH 3 I powder and PbI 2 (Aldrich) were reacted in a solvent of gamma-butyrolactone: dimethyl sulfoxide (7: 3) at 60 ° C for 12 hours to give a solution of CH 3 NH 3 PBI 3 wt%). The CH 3 NH 3 PBI 3 solution was deposited on the mp-TiO 2 / bl-TiO 2 / FTO substrate by two steps of spin coating (1000 rpm / 90 sec and 5000 rpm / 30 sec) 1 mL was added dropwise onto the substrate. The substrate was dried on a hot plate at 100 DEG C for 10 minutes.
For the deposition of the hole transport layer, the compound prepared in the above Example or Comparative Example was dissolved in toluene to prepare a 10 mM solution. To this solution was added 10 μl Li-bis (trifluoromethanesulfonyl) imide (Li-TFSI) / acetonitrile (170 mg / 1 mL) and 5 μl TBP as an additive. The solution was spin-coated on CH 3 NH 3 PBI 3 / mp-TiO 2 / bl-TiO 2 / FTO substrate at 3000 rpm for 30 seconds. Finally, a Au counter electrode was deposited by thermal evaporation. The active area of the electrode was fixed at 0.16 cm < 2 >.
2) Performance evaluation of solar cell
Short-circuit current density-Open-circuit voltage (JV curve) was measured using a solar simulator (Newport, Oriel Class A, 91195A) and a source meter (Keithley 2420) at 100 mA / NREL). The J-V curve was measured by masking the active area with a 0.096 cm2 metal mask. From this, the short circuit current density (Jsc), the open circuit voltage (Voc), the open circuit voltage, the FF factor and the power conversion efficiency (PCE) were measured. Table 2 and Fig.
As shown in Table 2 and FIG. 2, the solar cell using the compound according to the present invention as the hole transport layer has a higher performance index and power generation efficiency than the solar cell using the compound prepared in Comparative Example as the hole transport layer . Accordingly, it was confirmed that the performance index and the power generation efficiency of the solar cell can be remarkably improved by the increased LUMO energy level of the compound according to the present invention.
Claims (9)
[Chemical Formula 1]
In Formula 1,
R 1 and R 2 are each independently C 1 -4 alkoxy.
Wherein R < 1 > and R < 2 >
compound.
Wherein R < 1 > and R < 2 > are methoxy.
compound.
[Chemical Formula 1]
(2)
(3)
In the above formulas (1) and (3)
R 1 and R 2 are each independently C 1 -4 alkoxy.
Wherein the molar ratio of the compound represented by Formula 2 to the compound represented by Formula 3 is 1: 4 to 6,
Gt;
The reaction is carried out in the presence of 1) sodium tert-butoxide or potassium tert-butoxide; 2) tris (dibenzylideneacetone) dipalladium (0) or palladium acetate (Pd (OAc) 2 ); And 3) tri-tert-butylphosphine.
Gt;
Characterized in that the reaction is carried out at from 80 to < RTI ID = 0.0 > 150 C. <
Gt;
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