TW201025693A - Tandem organic solar cell - Google Patents

Abstract

The invention provides a tandem organic solar cell. The tandem organic solar cell comprises: an anode and a cathode; at least two photoactive layers disposed between the anode and cathode, wherein at least one of the photoactive layers comprises a soluble polythiophene derivative; and at least a separate layer, wherein the separate layer is disposed between the photoactive layers.

Description

201025693 IX. Description of the Invention: [Technical Field] The present invention relates to a serial/parallel type organic solar cell, and more particularly to a string/parallel type organic solar cell having a high open circuit voltage. [Prior Art] In recent years, due to the rise of environmental awareness and the exhaustion of energy, the development of solar cells has begun. The current solar cells can be classified into four types according to different materials: 'Shixi Semiconductor, Compound Semiconductor, Organic Semiconductor, and Dyestuff. Sensitized solar cells. Organic solar cells have received much attention in recent years due to their low cost, ease of manufacturing, and the advantages of being applicable to soft materials. However, the efficiency is not the same as the bottleneck that hinders the commercialization of organic solar cells. The problem lies in the range and low carrier transmission speed. This technology has no fatal injury. Compared with the solar spectrum, it covers 3G~4G% of the solar spectrum. (Investigate the thickness of the component (4) factors, the factors directly affect the light of the component: the use rate of the second is reduced. 'The efficiency of these components is improved. There are many ways to make the material of the string/parallel structure and the high-energy unit cell. (10) ee „) via series or parallel = is composed of multiple: stacking of multi-layer materials, overcoming the migration of carrier transport:, by not being able to make thick congenital _; also borrowing too low 'the thickness of the piece can not be hunted The gap material is used to match the 201025693, which increases the solar spectrum absorption range of the component, thereby effectively improving the overall efficiency of the component. By increasing the component structure, the solar spectrum absorption range is increased. So far, this technology is considered to improve the photoelectric conversion efficiency of the organic solar cell. The most advantageous method. US Patent No. 2007/0272296 proposes a tandem solar cell with at least two layers of active layers and A shared electrode is formed, wherein the shared electrode is prepared by a solution process. US Patent No. 20070246094 also proposes a tandem solar cell in which the type of the separation electrode (corresponding to the shared electrode of the above patent) is made. In more detail, the material of the active layer of light is expanded into an inorganic semiconductor material. In order to solve the problems encountered in current organic solar cells, it is urgent to propose an organic solar cell with high efficiency. A tandem organic solar cell comprises the following structures: an anode and a cathode; at least two photoactive layers, wherein at least one of the photoactive layers comprises a soluble polythiophene derivative. And a photoactive layer interposed between the anode and the cathode; and at least one intermediate layer, wherein the intermediate spacer layer is interposed between the photoactive layers. And other purposes, features, and advantages are more apparent and easy to understand. The embodiment and the accompanying drawings are described in detail as follows: 201025693 [Embodiment] The so-called tandem/parallel type organic solar cell (tandem cell) can be divided into two types: one type is tandem type (series tandem) The solar cell, the other is a parallel tandem solar cell, the difference between the two is the way of the line connection. If the two single cells are connected in series, it is a tandem solar cell, if it is from the middle of the two cells The anode and cathode are connected as a parallel type solar cell. Although the present invention and the drawings are of a tandem type, the scope of protection of the present invention is not limited to the tandem type solar cell, and the parallel tandem is used. Solar cells are also included in the scope of the invention to be protected. 1 is a schematic diagram of a high open circuit voltage/parallel organic solar cell 100 of the present invention. The structure mainly includes an anode 110 and a cathode 120; a first photoactive layer 214, A second photo active layer 224 is located between the anode 110 and the cathode 120; an intermediate layer 216, 222 is located between the first photo active layer 214 and the second photo active layer 224. In addition, the solar cell 100 In addition, a hole transport layer 212 is disposed between the anode 110 and the first light active layer 214, and an optical spacer 226 is disposed between the second light active layer 224 and the cathode 120. In the above structure, the front cell 210 is composed of the hole transport layer 212, the first photo active layer 214 and the intermediate spacer layer 216, and further comprises an intermediate spacer layer 222, a second photo active layer 224 and an optical spacer layer 226. Rear battery 220 (backcell), the tandem/parallel type organic solar cell 100 of the present invention is formed by a combination of two batteries. 20107 201025693 The anode 110 and the cathode 120 of the present invention are used as external connection electrodes for transmitting electrons. The anode 110 includes silver (silver, Ag), gold (gold), copper (copper, copper), indium tin oxide (ITO), tin oxide, zinc oxide (zinc oxide) ), doped with aluminum oxide (AZO), fluorine doped tin oxide (FTO) or conductive polymer (conductive polymer) and cathode 120 including gold (gold) , Au), silver (silver, Ag), copper (copper,

Cu), Ming (aluminum, Al), nickel (nickel, Ni), platinum (platinum, Pt), titanium (titanium, Ti), fluorinated clock (LiF), about (calcium, Ca), doping oxidation Aluminum doped zinc oxide (AZO), fluorine doped tin oxide (FTO) or a combination thereof. Further, a composite structure in which an interfacial layer/metal is combined may also be used as the anode 110 or the cathode 120 of the present invention, wherein the interface layer is, for example, a polymer compound such as poly(ethylene oxide). PEO) or polyfluorenes, or inorganic compounds such as cesium carbonate (Cs2C03) or calcium acetylacetonate (Ca(acac)2). Between the anode 110 and the cathode 120, at least two layers of photoactive layers are included. For simplicity of description, only two layers of photoactive layers are formed in FIG. 1, but in reality, it is not limited to two layers of active layers. The skilled person can prepare a light active layer on three layers to form a stacked combination of three or more batteries, wherein the two active layers 214, 224 are located at the anode 110 and the cathode 120, as required by the process. And wherein at least one of the light active layers comprises a soluble polyphenanthene derivative. 201025693 The active layer 214, 224 of the present invention comprises an electron acceptor material and an electron donor material, wherein the electron acceptor material is, for example, fullerene (C60), rich Fullerene derivation (eg phenyl-carbon 71-butyric acid brewing (pc71bm) or BenQ_Gap 61-butyric acid methyl ester (PC6ιΒΜ)), carbon nanotubes or other A compound having a strong eiectron withdrawing capability. The electron donor material is, for example, a soluble polythiophene derivative, poly(3-hexylthiophene) (P3HT), polyanline, polythiophene, polyvinylcarbazole, polydecane (polyvinylcarbazole). P〇lysiiane), polybenzothiazole or polybenzoisothiazole. In accordance with the present invention, at least one of the photoactive layers 214, 224 comprises a soluble polythiophene derivative as an electron acceptor. The soluble polythiophene derivative of the present invention has a structure of the formula (〖) or (11):

Formula (I ) ^ (Π) wherein R is hydrogen; alkyl; hydroxy; halogen; cyano (-CN); nitrite (-N〇2); amine; substituted or unsubstituted aryl; Unsubstituted heteroaryl group.

Ar is a substituted or unsubstituted aromatic hydrocarbon or heteroaromatic hydrocarbon group; and m and η are the number of repeating units, wherein m is preferably between 2 and 1 Torr, and 201025693 η is preferably between 〇 and loo. The above aromatic groups include phenyl (Phenyl), naphthyl, Diphenyl, Anthryl, Pyrenyl, Phenanthryl and Dibenzopentacyclic (Fluorene). Or other forms of polyphenyl ring substituent biphenyl.

The above heteroaromatic groups include Pyrane, Pyrroline, Furan, Benzofuran, Thiophene, benzoxanthene (361120^)1丨〇卩116116), Benzene sells two saliva (36112〇1:111〇(^2〇16), Pyridine, Quinoline, isoquinoline, pyrazine , Pyrimidine, Pyrrole, Pyrazole, Imidazole, Indole, Thiazole, Isothiazole, ° Oxazole, Isoxazole, Benzothiazole, Benzoxazole, 1,2,4-three chewing (l,2,4-Triazole), 1,2,3·三Tri(l,2,3-Triazole), Phenanthroline, Oxadiazolopyridine, 0-bite and Pyridopyrazine, benzo Benzooxadiazole, Thiadiazolopyridine, Selenophene, Thiadiazoloquinoxaline, Thienopyrazine, ^^^( Quinoxaline And diketopyrrolopyrrole or other forms of heteronuclear aromatic rings. The above aromatic hydrocarbon group may be various divalent groups of the above aromatic group; and the above heteroaromatic hydrocarbon group may be the above heteroaromatic Various divalent groups of the genus group. The soluble polythiophene derivative of the present invention may be a 201025693 copolymer (i.e., η greater than 1) or a monomer (i.e., η is equal to 0). In the formula, wherein R is a phenyl group or an alkylphenyl group, and Ar is a sulfur-containing heteroaromatic hydrocarbon group, such as: sinter, bisporphin, Benzothiodiazole (ΒΤ), 叹二β啥嗔# (Thiadiazoloquinoxaline, TQ) ' ^ (Thienopyrazine, Tp), representative combination of Quinoxaline (Q) grade 〆

Object:

Diketopyrrolopyrrole (DPP). The following table lists several polythiophene derivatives of the present invention. R Ar structural formula P18 hexyl phenyl porphin, benzothiadipine P21 hexyl dihexyl-C6 "13 .Η. M s phenyl Hexaphene S^CeHi3 P25 hexyl phenyl porphin, sigh two sputum scorpion 201025693 P27 hexane phenyl porphin, thiophene and ° P27 P29 hexane-based horn, CeHl3Wv ^CeHis Ο ( Λ phenyl quinoxaline CeHl3^ ^CeH13 Ρ29 P31 hexyl porphin, phenyl diketone ° 嘻 and 0 ratio slightly / /: NCeH13 J P31

In one embodiment, the first photoactive layer 214 of the present invention is a soluble polythiophene derivative blended with PC^BM or PC^BM, and the second photoactive layer 224 is P3HT and PC^BM. In a preferred embodiment, both layers of photoactive layers 214, 224 are comprised of a soluble polythiophene derivative and PC7iBm. In the photoactive layer of the above embodiment, the ratio of the electron donor to the electron acceptor is about 1:0.1 to 1:10, preferably 1:5 to 1:4. The above-mentioned hole transport layer 212 located in the front battery 210 serves to facilitate the transmission of the hole, which includes copper phthalocyanine (CuPc), ruthenium, Ν'-bis(1-naphthyl)-4. , 4'-biphenyldiamine (N,N'-di(naphthalen)-N,N'-diphenyl_benzidine,]SfPB), N-vinyl carbazole (PVK), vanadium pentoxide (V2〇5), three 12 201025693 Molybdenum oxide (Mo〇3), poly 3,4-ethyldioxythiophene: poly(3,4-ethylenedioxythiophene):poly(styrene-sulf〇 Nate), PEDOT: PSS) or other material with the ability to transmit holes. In one embodiment, the hole transport layer 212 is preferably poly(3,4-ethyldioxo): poly(p-styrenesulfonic acid) (PEDOT: PSS).

❹ The above mentioned optical spacer 226 between the active layer 224 and the cathode 120, the main function of which is to limit the light to the active layer of light to increase the use of light by the active layer. In general, The refractive index of each layer of the organic solar cell is not much different, and the light active layer 224 and the cathode 120 are separated by a low refractive index material, so that the light active layer 224 optically forms a light guiding layer, and the incident light is laterally absorbed by the light active layer 224. effectiveness. The material of the optical spacer 226 is, for example, a material such as titanium oxide (Ti〇x), tin oxide (Sn〇x) or zinc oxide (Zn0). Here, it should be noted that as long as the refractive index is lower than that of light The active layer material can be used as an optical separation layer, and is not limited to the materials mentioned above. In addition, the optical separation layer 226 may additionally be a hole barrier layer (hGleblGeking), which can block the transmission of the hole. The electronic intermediate separation layer I 222 is at least larger than the two layers, and is:: junction: real area =... The person can be separated by layers and is not limited to two layers, the skill: 'zinc oxide or indium tin oxide _) two = two == And the metal oxide spacer 222 modified by the second material is a germanium semiconductor material, for example, 13 201025693 3, 4-ethyldioxythiophene (PED〇T), vanadium pentoxide (V2〇5) Or molybdenum trioxide (M0O3) 'However, the second intermediate separation layer 222 is not limited to the materials mentioned above, and may be other materials having a hole transporting function. The invention utilizes two sets of cells to form a string/parallel type solar cell, and since the spectral absorption range of the two layers of the active layer is complementary, the component performance of the battery can be improved, and further, since the soluble polythiophene derivative has a coplanarity a group, which can increase the degree of conjugation between molecules to help the 冗 兀 force between molecules, so by using the soluble polyphenanthrene derivative of the present invention as a light active layer, thereby improving the device performance, especially in application In the case of a string/parallel solar cell structure, the open circuit voltage of the component is at least greater than 1.2 V. The soluble polythiophene polymer of the present invention is synthesized by the method of (〇rg. Lett 2006, 8, 5033-5036.) to synthesize thiophene-p-phenylene-thiophene-phenylene-thiophene, p-ATPT. Or a porphin-p-phenylene-thiophene via a Stiller coupling reaction, adding three (Tris(dibenzylideneacetone)-dipalladium) and three during the reaction. Tri(o-tolyl) phosphine is used as a catalyst in a chlorobenzene solvent. After the oxygen removal step, the polymerization is carried out in a microwave reactor, followed by a filtration and purification step. , a copolymer is obtained. For the serial/parallel organic solar cell of the present invention, please refer to FIG. 1 , and the preparation steps are as follows: 14 201025693 1. For example, the directly purchased IT0 electrode is used as the anode, and is first cleaned with main detergent, acetone and iso (10). The electrode is then dried to treat the electrode oxygen plasma. ^ nm hole transport layer '200 ° C temperature drying 2. Apply a thickness of about 1 〇 ~ 1 〇〇 212 coating on the anode 11 ,, followed by 1 〇〇 Qc baked about 8 ~10 minutes. 3. In the glove box, the first active layer 214 material is applied to the hole transport layer 212 in a coating manner, wherein the first active layer 214 has a thickness of about 30 to 200 nm. 4. Apply the intermediate separation layers 216, 222 to the first light active layer 214 in a coating manner, and bake in the air 7 (rc~8 (bake for 8 to 1 minute in rc, where the middle is separated) The thickness of the layers 216, 222 is about 5 to 7 〇 nm. 5. The first optical active layer 224 is applied on the intermediate spacer layer φ 222 by coating, wherein the coating thickness of the second active layer 224 is about It is 1 〇 22 22 nm. 6. An optical separation layer 226 having a thickness of about 1 〇 to 7 〇 nm is applied on the second light active layer 224 by coating, followed by 7 〇 in the air. ~8 (bake 8 to 10 minutes under rc. 7) in a steaming mode, a cathode 120 having a thickness of about 80 to 100 nm is plated on the optical separation layer 226 under a vacuum of 1 χ 10_7 to 5 x 10 7 torr, After the not: ~ 150. (: under annealing for about 25 to 30 minutes, the final component is completed by UV plastic packaging. 15 201025693 The above mentioned coating method, which means the solution process, the coating method includes spin coating (spin coating), bar coating, dip coating, roller coating, spray coating, concave Gravure coating, ink jet printing, slit coating (slot (3)) or knife coating ° The resulting tandem/parallel organic solar cell is then passed through the efficiency. Measurement #Measure, measure its open circuit voltage (v〇e), short circuit current (jsc), fill factor (ff), where the open circuit voltage value is greater than 1.2 v, and the short circuit current is about 4.0 to 9.0 mA / cm, the fill factor is approximately 40%~7〇〇/0. In one embodiment, when the two layers of the active layer are all using the soluble polyphenanthene derivative of the present invention, the tandem/parallel organic solar cell is preferably up to 15 v, indicating that the two-layer soluble polyphenanthrene derivative of the series/parallel 4 can improve the performance of the battery, and has great potential to become a commercial product in the future.

[Preparation Example] Only the compound 1 is synthesized, and the compound is extended to the phenyl group, Ατρτ) compound S5.

16 201025693

Scheme 1 describes the procedure for the preparation of compound S5. Compound 7 was prepared by a literature method, and the detailed preparation method is described in the literature (〇rg. Lett. 2006, 8, 5033-5036.). Take the magnesium tablets (1.2 g, 50 mmol) and a small amount of (ι2) into a 250 mL double-necked round bottom bottle, and connect the addition funnel and the condenser. Anhydrous tetrahydrogenate (50 mL) and 4-bromo-hexylbenzene (10.2 mL, 50 mmol) were injected into the addition funnel, respectively, and the reaction was started by dropping a few drops, followed by dropwise addition. In the middle of the flight, heat up to reflux after the drop. After the magnesium flakes had completely disappeared, Compound 7 (3 2 g, 8.3 mmol) was dissolved in 20 mL of anhydrous tetrahydrofuran into the addition funnel and dropped into the reaction flask under reflux. After the reaction, the mixture was cooled to room temperature, extracted with ethyl acetate, evaporated over anhydrous magnesium sulfate, filtered, and the filtrate was concentrated under reduced pressure to give a viscous yellow liquid compound. The viscous yellow liquid compound 17 prepared above was placed in a 25 〇mL single-necked round bottom bottle. '1 〇〇 mL of acetic acid was added, and after heating to 80 ° C, 5 mL of concentrated sulfuric acid was slowly added, and after reacting for 4 hours, The mixture was cooled to room temperature, extracted with ethyl acetate, and dried over anhydrous magnesium sulfate, filtered, and the filtrate was concentrated under reduced pressure, and then purified by column chromatography (cerium dioxide, 〇2, hexane) to obtain a yellow solid product. Compound 18 (3.2 g, 42%). Compound 18 (907 mg, 1 mmol) and N-brominated diimenimine (NBS) (392 mg, 2.2 mmol) were placed in a 1 mL round neck round bottle, plus 201025693 into 30 mL. The three gas chambers were wrapped in aluminum foil and immersed in ice water. After the reaction was carried out under nitrogen overnight, the mixture was extracted with chloroform and brine, and then organic layer was taken to remove water from anhydrous magnesium sulfate. The filtrate was concentrated under reduced pressure and then re-precipitated with methanol to obtain a pale yellow powder solid compound S5. (980 mg, 92%) 〇Compound 18: bNMRCCDCIsJOOMHz) δ 0.87 (t, J=6.6 ❿ Hz, 12H), 1.27~1.29 (m, 24H), 1.76 (m, 8H), 2.54 (t, "/= 8·0 Hz, 8H), 6.99 (d, 5.2 Hz, 2H), 7.09 (dd, 14.0, 8.0 Hz, WH), 7·23 (d, J = 4.8 Hz, 2H), 7.42 (s, 2H) . Compound S5: 4 NMR (CDC13, 200 MHz) δ 0.87 (t, J = 6.6 Hz, 12H), 1.29 (m, 24H), 1.57 (m, 8H), 2.56 (t, 8.0 Hz, 8H), 6.99 ( s, 2H), 7.07~7.09 (m, 16H), 7.32 (s, 2H). _ Preparation 2 Synthesis of thiophene-p-phenylene-thiophene (m-ATPT) compound compound S6 stream light 2

THF, reflux 65°C 201025693

Scheme 2 describes the procedure for the preparation of compound S6. According to the preparation method of the compound 18, the compound 13 (386 mg, 1.0 mmol) is used as a reactant.

Compound 22 was obtained, followed by a pale yellow powdery solid compound 23 (435 mg, 48%). Compound 23 (907 mg, 1 mmol) and N-bromosuccinimide (NBS) (392 mg, 2.2 mmol) were then placed in a 1 mL mL round neck bottle. Add 30 mL of tri-methane. The entire reaction flask was wrapped in aluminum foil and immersed in ice water. After the reaction was carried out under nitrogen overnight, the organic layer was extracted with trichloromethane and saturated brine. Water was removed from anhydrous magnesium sulfate, filtered, and the filtrate was concentrated under reduced pressure, and then re-precipitated with decyl alcohol to obtain a pale yellow powder solid. Compound S6 (586 mg, 550/〇). Compound 23: ^NMR (CDC13, 200 ΜΗζ) δ 0.84~0.91 (m, 12H), 1.28~ (m, 24H), 1.54 (m, 8H), 2.52 (t, J = 8.0 Hz, 8H), 6.93~7.08 (m, 18H), 7.28 (d, 5.2 Hz, 2H), 7.39 (s 1H), 7.52 (s, lH). , Compound S6 : hNMR (CDC13, 200 MHz) δ 0.84~0.91 (m, 12H), 1.28 (m, 24H), 1.54 (m, 8H), 2.51 (t, J = 8.2 Hz, 8H), 6.93-7.03 (m, igH)? 7 28 (d, 5.2 Hz, 2H), 7.34 (s, 1H), 7.37 (s, 1H). ' 19 201025693 ♦. Preparation Example 3 Synthetic Polymer P18 Process 3

Scheme 3 illustrates the step of preparing polymer P18. In a 500 ml glass reaction flask, put 0.15 mmole of p-thiophene-p-phenyl-thiophene (p-ATPT) and 0.3 mmole of 2,5-bis-trimethyltin sin 2,5-Bis-trimethylstannylthiophene and 0.15 mmole 4, 7-二漠-2,1,3-1,3-benzopyrene 2° sitting (4,7 1)1*〇111〇-2,1,3 56112〇1:10&(^2〇16,61') Three kinds of monomers, the catalyst is tris(dibenzylideneacetone) dipalladium (5.5 mg, 2 mol %) > tri(o-tolyl) phosphine (tri(o-tolyl) phosphine) 14.6 mg, 16 mol0/〇) and 5 ml of chlorobenzene. After the deoxygenation step, the reaction flask was placed in a microwave reactor for polymerization (640 W, 30 min). After returning to room temperature, the solution was dropped into methanol (MeOH) to precipitate a precipitate, which was filtered. The polymer was purified by methanol, acetone and hexane extraction to obtain a Pis polymer having a molecular weight of 38650 g/mol and entering „^= 55911111 (film). Preparation Example 4 Synthesis of Polymer P21 201025693

Scheme 4 describes the procedure for preparing polymer P21. In a 5 μm glass reaction flask, 0.3 mmole of p-thiophene-p-stabilized _thiophene (p_ATPT) φ and 0·3 mmole 2'', 5'''-bis-trimethyltin _5,5,,, ,,····································································· ',2''';4''',2,",;5,,,,,2,,,,,] sexithiophene two monomers, the catalyst is three (dibenzylideneacetone) two ( Tris(dibenzylideneacetone)dipalladium)(5.5 mg, 2 mol %) j Tri(o-tolyl)phosphine (14.6 mg, 16 mol%) and 10 ml of chlorobenzene, deoxygenated After the step, the reaction flask was placed in a microwave reactor for polymerization (640 W, 30 min), returned to the chamber φ temperature, and the solution was dropped into methanol (MeOH) to precipitate a precipitate, which was filtered, using methanol, acetone, and hexane. Soxhlet extraction cleaning polymer can obtain P21 polymer with molecular weight of 31587 g/mol and Xmax=486nm (film). Preparation Example 5 Synthesis of polymer P25 Process 5 21 201025693

Scheme 5 describes the procedure for preparing polymer P25. In 5〇〇mi glass

The reaction flask was placed in 〇·15 mmole of thiophene-p-phenyl-thiophene (p-ATPT) and 3.3 mmole 2,5-bistrimethyltinthiophene 2,5-Bis-trimethylstannylthiophene and 0.15 mmole 6,7 -dihexyl_4,9_dibromo[2,1,5]indole [3,4g]啥° 嘛 quinoxaline (6,7-Dihexyl-4,9-dibromo[2,l,5]thiadiazolo[ 3,4g] quinoxaline) three monomers, the catalyst is tris (dibenzylideneacetone) dipalladium (5.5 mg, 2 mol %) > tri-o-tolylphosphine (tri(o- Tolyl) phosphine) (14.6 mg, 16 mol%) and 10 ml of chlorobenzene' After the oxygen scavenging step, the reaction flask was placed in a microwave reactor for polymerization (640 W, 30 min). After returning to room temperature, the solution was added dropwise to methanol (MeOH) to precipitate a precipitate, which was filtered. The polymer P25 polymer, λ, was purged by methanol, acetone, and hexane. ^ Production 1179nm (film). Preparation Example 6 Synthesis of Polymer P27 Process 6 201025693

Stille coupling polymerization • Scheme 6 describes the procedure for preparing polymer P27. In a 5 μm glass reaction flask, put 0.15 mmole of porphin-p-phenylene porphin (ρ ΑΤρτ) and 0.3 mmole of 2,5-bistrimethyl porphin 2,5-Bis-trimethylstannylthiophene and 0.15 mmole. 5,7-dibromo-2,3-diphenyl thiazepine [3,7-dibromo-2,3-Diphenylthieno[3,4-b]pyrazine) The catalyst is Tris(dibenzylideneacetone) dipalladium (5.5 mg, 2 mol %) * ® tri(o-tolyl) phosphine (14.6 mg, 16 mol%) and 10 ml of chlorobenzene. After the oxygen removal step, the reaction flask was placed in a microwave reactor for polymerization (640 W, 30 min). After returning to room temperature, the solution was added dropwise to methanol (MeOH) to precipitate a precipitate, which was filtered. The polymer was washed with methanol, acetone and hexane to obtain a P27 polymer having a molecular weight of 20056 g/mol and Xonset = 1170 nm (film). Preparation Example 7 Synthesis of Polymer P29 Process 7 201025693

Stille coupling polymerization Flow 7 describes the step of preparing polymer P29. In a 500 ml glass reaction flask, put 0.15 mmole of thiophene-p-phenylene-thiophene (p-ATPT) and 0.3 mmole of 2,5-bistrimethylstannylthiophene 2,5~^5- dozen 111^1 ;11>^1 牡111^11;1^〇卩116116 and 〇.15 111111〇16 5,8-dibromo-2,3-diphenyl 啥 琳 ( (5,8-dibromo-2,3-Diphenylquinoxaline The three monomers 'catalysts are tris (dibenzylideneacetone) dipalladium) (5.5 mg, 2 mol %) » tri-o-tolyl phosphine (14.6) Mg, 16 mol%) and

10 ml of chlorobenzene, after the oxygen removal step, the reaction flask was placed in a microwave reactor for polymerization (640 W, 30 min). After returning to room temperature, the solution was added dropwise to methanol (MeOH) to precipitate a precipitate, which was filtered. The polymer was washed with methanol, acetone, and hexane to obtain a P29 polymer having a molecular weight of 14229 g/mol and konset = 690 nm (film). Preparation Example 8 Synthesis of Polymer P31 Process 8 24 201025693

Scheme 8 describes the procedure for preparing polymer P31. In a 500 ml glass reaction flask, put 0.15 mmole of porphin-p-phenylene-shen (p_ATPT) and 0.3 mmole of 2,5-bistrimethyltin sin 2,5-Bis-trimethylstannylthiophene and 0.15 mmole 3, 6, bis-(5-bromo-thiophene)-2,5-bis-(2-ethyl-hexyl)pyrrole [3,4-c]pyrrole-1,4-dione (3,6-Bis-( 5-bromo-thiophen-2-yl)>2,5-bis-(2-ethyl-hexyl)pyr rolo[3,4-c]pyrrole-l,4-dione) three monomers, three catalysts (Tris(dibenzylideneacetone) dipalladium) (5.5 mg, ❿ 2 mol %), tri(o-tolyl) phosphine (14.6 mg, 16 mol%) And 10 ml of chlorobenzene, after the oxygen removal step, the reaction flask was placed in a microwave reactor for polymerization (640 W, 30 min). After returning to room temperature, the solution was added dropwise to methanol (MeOH) to precipitate a precipitate, which was filtered. The polymer was cleaned by methanol, acetone, hexane, and the amount of the polymer was 28,589 §/111〇1, human. 11 such as =90411111 (film)? 31 polymer. [Examples] Example 1 25 201025693 The following describes the fabrication process of each layer: 1. Anode and hole transport layer: The glass-lined (as anode) cleaning step is washed with detergent, acetone and isopropyl alcohol, respectively, followed by drying. glass. Prior to coating the hole transport layer PEDOT:PSS (Baytron Ρ ΑΙ 4083), the ΙΤΟ glass was first treated with 〇2-plasma. After coating, the ped〇T:PSS layer was baked at 140 ° C for 1 〇. 2. The first active layer: P18 (0.5wt%) is matched with PC7〇BM (1.5 φ wt%), which is configured as the first active layer material in a ratio of 1:3 (wt%), and the P18 is active in the glove box. The layer material (using o-dichlorobenzene (〇_dichl〇r〇benzene) as a solvent) was spin coated on the PED0T hole transport layer. 3. Intermediate separation layer: first take the TiOx precursor solution and dilute it in air with 'methanol' onto the first active layer by spin coating (speed 6 rpm). Then in the air. 80 〇c grilled for 1 minute. PEDOT:PSS (蹲 from Baytron PH500) was then applied over the TiOx layer, which was about 40 nm thick, and the components were then placed in a glove box and baked at 80 φ °C for 10 minutes. 4. The second active layer: P3HT (1 wt%) with PC71BM (0.7 wt%) was spin-coated on top of the intermediate separator with trichloromethane (CHCI3) as solvent. 201025693 成. Finally, the structure of the entire series/parallel type organic solar cell is as follows: ITO/PEDOT/P18: PC7iBM/TiOx/PEDOT/P3HT: PC7iBM/TiOx/A1. The efficiency of the battery of Example 1 is as follows: Table 1: Table 1

Jsc (mA/cm2) Voc (V) FF (%) η (%) Example 1 (serial/parallel battery) 6.17 1.33 56.0 4.60 single battery (P18: PC?iBM) 8.74 0.81 52.8 3.72 single battery (P3HT : PC7iBM) 8.47 0.62 59.6 3.11 The short-circuit current of Example 1 is about 6.17 mA/cm2, the fill factor is about φ 56%, the photoelectric conversion efficiency is about 4.60, and the open circuit voltage is about 1.33 V, compared to the single cell. The value (0.807 V, 0.617 V) is higher. Example 2 The preparation method of Example 2 is the same as that of Example 1, except that the second photoactive layer is also composed of P18: PC71BM (1:3) dissolved in chlorobenzene, and the efficiency of the components is as follows. 2 : 27 201025693 Table 2

Jsc (mA/cm2) Voc (V) FF (%) η (%) Example 2 (string/parallel battery) 5.06 1.51 45.8 3.51 single cell (P18: PC71BM) 8.60 0.81 53.0 3.68 single cell (P18: PC ?iBM) 7.64 0.79 49.0 2.97 The open circuit voltage of this embodiment is higher than that of the first embodiment (about 1.51 V), indicating that the battery can be improved by using the soluble polythiophene derivative as the two-layer active layer. Performance. Example 3 The preparation method of Example 3 is the same as that of Example 1, except that the first photo active layer is composed of P31: PC61BM (1:3.5) dissolved in chlorobenzene, and the efficiency of the element φ is as follows: table 3

Jsc (mA/cm2) Voc (V) FF (%) η (%) Example 3 (string/parallel battery) 6.66 1.30 50.5 4.42 Single battery (P31: PC61BM) 8.33 0.74 52.8 3.26 Single battery (P3HT : PC71BM 8.66 0.60 56.5 2.93 28 201025693 The open circuit voltage value of this embodiment is about 1.30V, which is higher than the value of the single cell (0.74 V, 0.60V). It can be seen that the serial/parallel type solar cell can be compared with the single cell. It has a better open circuit voltage. In addition, the short-circuit current is about 6.66 mA/cm2, the fill factor is about 50.5%, and the photoelectric conversion efficiency is about 4.42. While the invention has been described above in terms of several preferred embodiments, it is not intended to limit the scope of the present invention, and it is possible to make any changes without departing from the spirit and scope of the invention. And the scope of the present invention is defined by the scope of the appended claims.

29 201025693 [Simplified description of the drawings] Fig. 1 is a cross-sectional view for explaining the structure of a string/parallel type solar cell of the present invention. [Main component symbol description] 100~string/parallel type organic solar cell 110~anode Φ120~cathode 210~front battery '212~hole transport layer 214~first light active layer 216, 222~intermediate separation layer 220~ Rear battery 224~second light active layer 226~ optical separation layer 30

Claims (1)

201025693 X. Patent application: 1. The tandem organic solar cell 'includes the following structure: an anode and a cathode; at least two photoactive layers, of which At least one layer of the light active layer includes a soluble polythiophene derivative, wherein the light active layer is between the anode and the cathode; and at least one intermediate layer, wherein the intermediate spacer layer is between the light 2. Between the active layers. 2. The serial/parallel organic solar cell as described in claim 1 wherein the open/parallel organic solar cell has an open circuit voltage of at least about 1.2 V. 3. The string/parallel type organic solar moon t* battery according to item 1 wherein the light active layer comprises an electron acceptor material and an electron donor material. 4. The tandem/parallel type organic solar cell as described in claim 3, wherein the electron acceptor material comprises fullerene (C6〇), phenyl-depleted 71-butyric acid methyl ester (PC) 7iBM), stupid base_carbon 61_methyl butyrate (PC61BM) or carb〇n nanotubes. 5. The tandem/parallel organic solar cell as described in claim 3 Wherein the electron donor material comprises the soluble polythiophene derivative, poly(3·hexanylthiophene) (P3HT), polyaniline (p〇lyanline), polythiophene, polyvinyl azole (p〇lyvinylcarbaz) 〇le), polysilane, polystyrene and polystyrene (p〇iybenz〇thiaz〇ie) or polybenzoxene 31 201025693 isobenzoisothiazole. As described in the scope of patent application 帛i a tandem/parallel type organic solar cell, wherein the soluble polythiophene derivative has a structure of the formula (1) or (π): Wherein R is hydrogen, alkyl, permeyl, arginyl, aryl (-CN), nitrite (-N〇2), amine, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl Ar is a substituted or unsubstituted aromatic hydrocarbon or heteroaromatic hydrocarbon group; and m and η are the number of repeating units, m is between 2 and 1 Torr, and n is between 0 and 100. ❹ 7. The tandem/parallel type organic solar cell as described in claim 6, wherein the aryl group includes a phenyl group (Phenyl), a naphthyl group, a diphenyl group, and an anthracene group (Anthryl). ), benzophenanthrenyl, Phenanthryl or dibenzopentacene (Fluorene). 8. The tandem/parallel type organic solar cell of claim 6, wherein the heteroaromatic group includes Pyrane, Pyrroline, Furan, benzopyran (Benzofuran), Thiophene, Benzothiophene, Benzothiodiazole, Pyridine, Quinoline, iso 32 201025693 喧#(isoquinoline), °pyrazine, pyrimidine, pyrrole, pyrazole, Imidazole, Indole, Thiazole, and sputum (Isothiazole), β Oxazole, Isoxazole, Benzothiazole, Benzoxazole, 1,2,4-trioxin (l, 2, 4-Triazole), 1,2,3-three-dimensional stagnation (l,2,3-Triazole), phenanthroline (Phenanthroline), ° Oxadiazolopyridine, ° bite ratio °Pyridopyrazine, Benzooxadiazole, Thiadiazolopyridine, Selenophene, sold two Thiadiazoloquinoxaline, Thienopyrazine, Quinoxaline or Diketone, and "Diketopyrrolopyrrole" 〇 9. As stated in the scope of claim 6 / Stacked organic solar cells, where η is greater than one. 10. The tandem/parallel organic solar energy cell of claim 6, wherein n is equal to zero. 11. The tandem/parallel type organic solar cell of claim 6, wherein the R is a phenyl group or an alkylphenyl group. 12. The tandem/parallel organic solar ti battery as described in claim 6 wherein the Ar is a sulfur-containing heteroaromatic cigarette radical. 13. The tandem/parallel type organic solar cell as claimed in claim 6, wherein the sulfur-containing heteroaromatic hydrocarbon group comprises thiophene, dithiophene or benzopyrene, and the sputum is sputum. (Thiadiazoloquinoxaline), 嗟 and 0it'^Thienopyrazine), Quinoxaiine or diketopoxime 33 201025693 Diketopyrrolopyrrole. 14. The tandem/parallel organic solar cell of claim 6, wherein the soluble polythiophene derivative has a molecular weight of from about 1 Å to about 10,000. 15. The serial/parallel organic solar cell as described in claim 1, wherein the anode comprises silver (Ag), gold (Au), copper (Cu), oxidized glass (ITO), and oxidized kick (tin oxide), zinc oxide, aluminum doped zinc oxide (AZO), fluorine doped tin oxide (FTO) or conductive polymer 16. The tandem/parallel type organic solar cell as described in claim i wherein the cathode comprises gold (Au), silver (Ag), copper (Cu), aluminum (A1), nickel (Ni), Platinum (Pt), titanium (Ti), lithium fluoride (LiF), calcium (Ca), aluminum doped zinc oxide (AZO), fluorine doped tin oxide (fluorine doped tin oxide, FTO ) or a combination of the above. ❿ 17. The tandem/parallel organic solar moon color battery according to claim 1, wherein the anode or cathode further comprises a composite structure in which an interface layer and a metal are combined. 18. The tandem/parallel type organic solar cell of claim 17, wherein the interfacial layer comprises polycyclohexane (pE0), polyfluorenes, carbonic acid planer (Cs2C03) or ethylene acetone acetone ( Ca(acac)2) 0 19. The tandem/parallel type organic solar cell of claim 1, wherein the intermediate separator comprises 3,4-ethyldioxythiophene (PEDOT), pentoxide Hunger (v2〇5) or trioxide|g(Mo03). The cross-column type organic solar cell of claim 1, wherein the intermediate separator further comprises a metal oxide. 21. The tandem/parallel organic solar cell of claim 20, wherein the metal oxide comprises titanium oxide, cerium oxide, zinc oxide or indium tin oxide (ITO). 22. The tandem/parallel organic solar cell of claim 1, wherein the photoactive layer and the intermediate spacer are prepared by a solution process. 23. The tandem/parallel type organic solar cell of claim 22, wherein the solution process comprises spin coating, bar coating, dip coating , roll coating, spray coating, gravure coating, ink jet printing, slot coating or knife coating (knife) Coating). 35