CN111704814B - Annealing-free high-conductivity molybdenum oxide coating capable of being processed in solution and preparation method of film - Google Patents
Annealing-free high-conductivity molybdenum oxide coating capable of being processed in solution and preparation method of film Download PDFInfo
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- 229910000476 molybdenum oxide Inorganic materials 0.000 title claims abstract description 63
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 238000000576 coating method Methods 0.000 title claims abstract description 34
- 239000011248 coating agent Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 238000000137 annealing Methods 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 16
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 11
- 239000003446 ligand Substances 0.000 claims abstract description 7
- 239000003960 organic solvent Substances 0.000 claims abstract description 7
- 238000007639 printing Methods 0.000 claims abstract description 6
- -1 diboron compound Chemical class 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 35
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 239000006185 dispersion Substances 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 7
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 6
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 6
- QXYJCZRRLLQGCR-UHFFFAOYSA-N dioxomolybdenum Chemical group O=[Mo]=O QXYJCZRRLLQGCR-UHFFFAOYSA-N 0.000 claims description 4
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 239000011733 molybdenum Substances 0.000 claims description 3
- BDEIASRRCFZGBR-UHFFFAOYSA-N B(O)(O)O.CC(C)(CC(C)O)O.CC(C)(CC(C)O)O Chemical compound B(O)(O)O.CC(C)(CC(C)O)O.CC(C)(CC(C)O)O BDEIASRRCFZGBR-UHFFFAOYSA-N 0.000 claims description 2
- SMTJVGKZVGURTO-UHFFFAOYSA-N B(O)(O)OB(O)O.OCC(C)(CO)C Chemical compound B(O)(O)OB(O)O.OCC(C)(CO)C SMTJVGKZVGURTO-UHFFFAOYSA-N 0.000 claims description 2
- 239000003153 chemical reaction reagent Substances 0.000 claims description 2
- 238000010790 dilution Methods 0.000 claims description 2
- 239000012895 dilution Substances 0.000 claims description 2
- 238000007641 inkjet printing Methods 0.000 claims description 2
- 238000007650 screen-printing Methods 0.000 claims description 2
- 238000004528 spin coating Methods 0.000 claims description 2
- 238000005507 spraying Methods 0.000 claims description 2
- 238000010345 tape casting Methods 0.000 claims description 2
- IVDFJHOHABJVEH-UHFFFAOYSA-N pinacol Chemical compound CC(C)(O)C(C)(C)O IVDFJHOHABJVEH-UHFFFAOYSA-N 0.000 claims 2
- SCWWDULYYDFWQV-UHFFFAOYSA-N (2-hydroxyphenoxy)boronic acid Chemical compound OB(O)OC1=CC=CC=C1O SCWWDULYYDFWQV-UHFFFAOYSA-N 0.000 claims 1
- 239000002019 doping agent Substances 0.000 abstract 1
- 239000010408 film Substances 0.000 description 37
- 239000000758 substrate Substances 0.000 description 20
- 239000011521 glass Substances 0.000 description 16
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 229920000301 poly(3-hexylthiophene-2,5-diyl) polymer Polymers 0.000 description 5
- UUIQMZJEGPQKFD-UHFFFAOYSA-N Methyl butyrate Chemical compound CCCC(=O)OC UUIQMZJEGPQKFD-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- FFRBMBIXVSCUFS-UHFFFAOYSA-N 2,4-dinitro-1-naphthol Chemical compound C1=CC=C2C(O)=C([N+]([O-])=O)C=C([N+]([O-])=O)C2=C1 FFRBMBIXVSCUFS-UHFFFAOYSA-N 0.000 description 3
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- QZEWCQGGAIGUPS-UHFFFAOYSA-N benzene-1,2-diol;boric acid Chemical compound OB(O)O.OC1=CC=CC=C1O.OC1=CC=CC=C1O QZEWCQGGAIGUPS-UHFFFAOYSA-N 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 239000003599 detergent Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 238000009987 spinning Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- HXVNBWAKAOHACI-UHFFFAOYSA-N 2,4-dimethyl-3-pentanone Chemical compound CC(C)C(=O)C(C)C HXVNBWAKAOHACI-UHFFFAOYSA-N 0.000 description 1
- BMIBJCFFZPYJHF-UHFFFAOYSA-N 2-methoxy-5-methyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyridine Chemical compound COC1=NC=C(C)C=C1B1OC(C)(C)C(C)(C)O1 BMIBJCFFZPYJHF-UHFFFAOYSA-N 0.000 description 1
- 229910015711 MoOx Inorganic materials 0.000 description 1
- 125000005595 acetylacetonate group Chemical group 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000010129 solution processing Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
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- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/24—Electrically-conducting paints
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- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—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
- H01L31/02—Details
- H01L31/0224—Electrodes
- H01L31/022466—Electrodes made of transparent conductive layers, e.g. TCO, ITO layers
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Abstract
The invention discloses a method for preparing a solution-processable high-conductivity molybdenum oxide coating without annealing and a film, which is characterized by comprising the following steps of: comprises the following steps of 1) preparing the hydrogen peroxide solution of the molybdenum oxide. 2) Adding a ligand solution containing a diboron compound to the solution prepared in step 1) to obtain a coordinated molybdenum oxide solution. 3) The coordinated molybdenum oxide obtained in the step 2) is used as a raw material of the coating. According to the invention, the coordination dopant is introduced into the molybdenum oxide solution, and the molybdenum oxide solution is dried and then dispersed in the organic solvent, so that the molybdenum oxide film can show better conductivity and lower roughness without annealing after being prepared into a film by a wet method. The preparation method has the advantages of easily available raw materials, simple preparation process, no need of high-temperature annealing and suitability for large-scale roll-to-roll printing.
Description
Technical Field
The invention relates to the field of semiconductor photoelectric materials, in particular to a solution-processable high-conductivity molybdenum oxide coating without annealing and a preparation method of a film.
Background
Optoelectronic devices, such as solar cells, typically require energy level modification using interface materials, including cathode interface layers and anode interface layers, due to the need to form ohmic contacts with the electrodes. Molybdenum oxide is typically used as the anode interfacial layer due to its higher work function.
Currently, molybdenum oxide is generally used to deposit a thin molybdenum oxide film on the active layer by evaporation coating, and this method is not suitable for mass production such as roll-to-roll printing due to the requirement of vacuum environment for evaporation coating.
In recent years, the preparation of soluble solutions of molybdenum oxide has been attracting more and more attention, and the most common method includes obtaining a molybdenum oxide thin film by high-temperature annealing after film formation using soluble precursors such as ammonium salts and acetylacetonates of molybdenum. Due to the characteristics of low conductivity and sensitivity to film thickness of molybdenum oxide, to meet the requirements of roll-to-roll printing production, the conductivity of molybdenum oxide needs to be improved by doping and the like, an n-type doping method is usually adopted, but the result brought by n-type doping can bring about the influence of light transmittance reduction besides the improvement of the conductivity, and high-temperature annealing is needed, so that the molybdenum oxide film which can be processed by solution at present is mainly applied to a positive device structure, and is formed into a film below an active layer, as shown in figure 1, the molybdenum oxide film is positioned between a transparent electrode and the active layer, and the light transmittance is reduced, so that the light utilization rate of the device is inevitably reduced. The problem of light transmission can be solved by developing a technology for forming a film of molybdenum oxide on the active layer by using an inverted structure device without high-temperature annealing. Molybdenum oxide coatings with high conductivity and without high temperature annealing are in urgent need to be developed in order to better meet the requirements of roll-to-roll printing.
Disclosure of Invention
The invention aims to provide a preparation method of a high-conductivity molybdenum oxide coating which can be processed by solution without annealing, and is characterized in that:
1) an aqueous solution of molybdenum oxide in hydrogen peroxide was prepared.
2) Adding a ligand solution containing a diboron compound to the solution prepared in step 1) to obtain a coordinated molybdenum oxide solution.
3) The coordinated molybdenum oxide obtained in the step 2) is used as a raw material of the coating.
2. The method of preparing a solution processable high conductivity molybdenum oxide coating without annealing as claimed in claim 1, wherein:
in the step 1), adding a solvent into a hydrogen peroxide solution of molybdenum oxide for dilution.
Further, in step 1): adding a solvent so that the concentration (mg/ml) of the molybdenum oxide is 1-20.
Further, in the step 1), the molybdenum oxide is selected from molybdenum dioxide or molybdenum trioxide.
Further, in the step 1), the solvent is selected from hydrogen peroxide, deionized water, ethanol, methanol, toluene, isopropanol, butanol, N-dimethyl sulfoxide and ethylene glycol methyl ether.
Further, in the step 1), the ratio (mg/ml) of the molybdenum oxide to the hydrogen peroxide solution is as follows: 40 to 80 parts by weight
Further, in step 2), the ligand solution is selected from pinacol ester diborate (CAS: 73183-34-3), bis (2-methyl-2, 4-pentanediol) borate (CAS: 230299-21-5), neopentyl glycol diborate (CAS: 201733-56-4), 4',5,5' -tetramethyl-2, 2' -bi-1, 3, 2-dioxaborole (CAS: 230299-23-7) and bis-catechol borate (CAS: 13826-27-2) one or more alcohol-soluble diboronic acid ester.
Further, in the step 2), the using amount of the ligand reagent is at least 0.01-300% of the mass of the molybdenum source.
Further, in the step 3), the coordinated molybdenum oxide solution obtained in the step 2) is dried to remove the solvent and then is dispersed in an organic solvent, and the dispersed product is a high-conductivity molybdenum oxide coating.
Further, the organic solvent is selected from one or more of isopropanol, methanol, ethanol, butanol, toluene, N-N-dimethyl sulfoxide and ethylene glycol methyl ether.
Further, the concentration range (mg/ml) of the dispersion was: 10 to 100.
The invention discloses a film preparation method taking the coating as a raw material, which is characterized by comprising the following steps: dispersing the coating raw materials in an organic solvent to prepare a dispersion liquid, and preparing the molybdenum oxide film by a wet preparation process.
Further, the wet preparation process at least comprises one of the following steps: spin coating, doctor blading, screen printing, slot coating, spray coating, ink jet printing or wire rod printing.
Furthermore, when the film is prepared by a wet method, the deposition of the active layer of the solar cell is firstly carried out to obtain the substrate with the active layer film. I.e., poly-3-hexylthiophene (P3HT) and [6,6 ]]-phenyl C61 butyric acid methyl ester (PC)61BM) were dissolved together in 1, 2-o-dichlorobenzene (oDCB) and stirred for 8 hoursObtaining a solution for later use. Among them, P3HT and PC61The mass ratio of BM is (1:0.8) - (1:1), and the ratio of the total mass of solute to the volume of solvent (mg: mL) is (16-20). The solution is used as a raw material, a film is prepared on a substrate and is annealed, and the substrate is used as a substrate with an active layer film.
The invention has the following advantages:
the invention designs a brand-new high-conductivity molybdenum oxide coating which does not need annealing and solution processing and a film preparation method, and the method can form a film on an organic or perovskite material and has higher conductivity. The method is simple to operate, low in cost of used raw materials and convenient for large-scale industrial production.
Drawings
Fig. 1 is a view showing the micro-morphology (AFM) of the molybdenum oxide thin films prepared in the example 2 and 3. Left side B-MoOXas cast is a molybdenum oxide film on conductive glass, B-MoO on the rightXAnd the on AL is a molybdenum oxide film on the organic active layer. The top two are AFM height (height) images and the bottom two are AFM phase (phase) images.
Fig. 2 is a schematic diagram of a solar cell structure.
FIG. 3 is a diagram showing the molybdenum oxide solution obtained in step 1) (left) and the redispersion obtained in step 3) (right) in example 1.
Detailed Description
The present invention is further illustrated by the following examples, but it should not be construed that the scope of the above-described subject matter is limited to the following examples. Various substitutions and alterations can be made without departing from the technical idea of the invention and the scope of the invention is covered by the present invention according to the common technical knowledge and the conventional means in the field.
Example 1:
this example is the coating feedstock preparation.
A preparation method of a high-conductivity molybdenum oxide coating capable of being processed in solution without annealing is characterized by comprising the following steps:
1) preparing a hydrogen peroxide solution of molybdenum oxide:
1.1) taking 80mg of molybdenum trioxide powder, adding 1mL of hydrogen peroxide solution, adding a magnetic stirring bar, stirring, and stirring at room temperature for 12 hours to obtain a yellow solution.
1.2) the yellow solution is heated and stirred for 3 hours at 60 ℃ to obtain a golden yellow clear solution.
1.3) the resulting clear golden yellow solution was diluted with 3mL of deionized water and filtered for use.
2) Preparation of coordinated molybdenum oxide:
2.1) taking 160mg of bis-catechol borate (BDB), adding 2ml of isopropanol, adding a magnetic stirrer to stir, and stirring for 3 hours at room temperature to obtain a clear and transparent BDB solution.
2.2) dropwise adding the golden yellow solution obtained in the step 1.3) into the BDB solution obtained in the step 2.1) under the stirring condition to obtain black green B-MoOXAnd (3) continuously stirring the solution (after coordination, the valence state of Mo is changed, the value of x is between 2 and 3 and is represented by an angle mark x) for 3 hours.
3) Obtaining the coating material
Mixing the B-MoO obtained in 2.2)XDrying the solution in a rotary evaporator or a freeze dryer, and removing the solvent to obtain black B-MoOXSolid powder raw material.
Example 2:
this example is the film formation of a molybdenum oxide coating on a glass substrate.
This example uses the starting materials described in example 1 for the preparation of film samples:
s1) glass substrate preparation
S1.1) placing pre-etched transparent conductive glass with the size of 15mm multiplied by 15mm on a polytetrafluoroethylene cleaning support, placing the support in a beaker, adding 120ml of deionized water and 5% -10% of detergent into the beaker, wherein the deionized water is just above the conductive glass substrate, performing ultrasonic cleaning for 10min, pouring out mixed liquid of the deionized water and the detergent, placing 120ml of new deionized water in the beaker, covering the beaker with tin foil paper, placing the beaker in an ultrasonic cleaner for cleaning, and repeating for 3 times.
S1.2) taking out the beaker, opening the tin foil paper, pouring out deionized water, putting 120ml of acetone into the beaker for cleaning, finally storing the conductive glass substrate in isopropanol for standby use, and covering the beaker with the tin foil paper.
S1.3) taking out the conductive glass substrate stored in the isopropyl ketone in the step 1.5), and drying by using high-purity nitrogen.
S1.4) placing the dried conductive glass substrate into a culture dish, placing the culture dish into an ultraviolet ozone treatment instrument, treating for 15min, and taking out.
S2) preparation of coatings
The B-MoO obtained in step 3) of example 1 was weighedX100mg of powder, 1ml of isopropanol is added, ultrasonic dispersion is carried out for 15 minutes, and then stirring is carried out for 12 hours to obtain B-MoOXAnd filtering the dispersion liquid for later use.
S3) spinning of the Dispersion
Placing the conductive glass substrate treated by ozone obtained in the step S1) at the center of a turntable of a spin coater, and uniformly covering 50 μ L of the B-MoO obtained in the step S2) on the conductive glass substrateXAnd (5) starting a spin coater to spin the film on the dispersion liquid. The spin rate of the spin coater was set at 3000rpm for 30 seconds. A sample film formed uniformly on the substrate was obtained.
Example 3:
this example is the film formation of a molybdenum oxide coating over an organic active layer film.
This example uses the starting materials described in example 1 for the preparation of film samples:
s1) preparing a glass substrate sheet in the same manner as in step S1 of example 2).
S2) dope preparation same as step S2 of example 2).
S3) deposition of active layers of solar cells
S3.1) 17mg of poly-3-hexylthiophene (P3HT) and 17mg of [6,6 ]]-phenyl C61 butyric acid methyl ester (PC)61BM) were dissolved together in 1ml of 1, 2-o-dichlorobenzene (oDCB) and stirred for 8 hours to give a solution ready for use.
S3.2) placing the glass substrate treated by the ozone obtained in the step S1) at the center of a turntable of a spin coater, dripping 20 microlitres of the solution obtained in the step 3.1) on the glass substrate to uniformly cover the glass substrate, and starting the spin coater to spin the film. The primary rotation speed of the spin coater is set to be 600rpm for 60s, the secondary rotation speed is set to be 1200rpm for 3 s.
S3.3) placing the film obtained in the step 3.2) at 120 ℃ for thermal annealing for 10 minutes.
S4) spinning of the Dispersion
Placing the substrate with the active layer film obtained in the step S3.3) at the center of a turntable of a spin coater, taking 50 microliters of dispersion liquid obtained in the step S2), dropwise adding the dispersion liquid onto the film, and starting the spin coater to spin the film. The rotation speed of the spin coater was set at 3000rpm for 30 s. A sample film formed uniformly on the substrate was obtained.
And (3) testing: for the B-MoO obtained in example 2XThe films were tested for film thickness, roughness and conductivity, and the results are shown in Table 1.
Wherein the control molybdenum oxide coating is the undoped molybdenum oxide solution obtained in step 1) of example 1, the control glass substrate preparation process is the same as step S1) of example 2, the coating process is the same as step S3) of example 2, and the mark is MoOx。
TABLE 1
| Molybdenum oxide type | Film thickness (nm) | Roughness (nm) | Conductivity S cm-1 |
| MoOX | 25.8 | 3.2 | 9.1E-7 |
| B-MoOX | 236 | 2.1 | 3.6E-5 |
The micro-morphology of the film formed by the molybdenum oxide coating on the conductive glass and the organic active layer film is respectively characterized by using an Atomic Force Microscope (AFM), and the micro-morphology is shown in figure 1.
From the above results, it is understood that the present invention can improve the conductivity and the solubility in alcohols by doping molybdenum oxide by means of coordination. The method is simple to operate, and more importantly, the higher conductivity and the smoother and uniform micro-morphology can be obtained without an additional post-annealing process, so that the method is convenient for large-scale industrial production.
Claims (6)
1. A preparation method of a high-conductivity molybdenum oxide coating capable of being processed in solution without annealing is characterized by comprising the following steps:
1) preparing a hydrogen peroxide solution of molybdenum oxide: adding a solvent into the hydrogen peroxide solution of the molybdenum oxide for dilution so as to ensure that the concentration of the molybdenum oxide is 1 mg/ml-20 mg/ml; the molybdenum oxide is selected from molybdenum dioxide or molybdenum trioxide;
2) adding a ligand solution containing a diboron compound into the solution prepared in step 1) to obtain a coordinated molybdenum oxide solution; the ligand solution is selected from one or more of pinacol diborate (CAS: 73183-34-3), bis (2-methyl-2, 4-pentanediol) borate (CAS: 230299-21-5), neopentyl glycol diborate (CAS: 201733-56-4), 4',5,5' -tetramethyl-2, 2' -bis-1, 3, 2-dioxaborole (CAS: 230299-23-7) and bis catechol borate (CAS: 13826-27-2); the ligand reagent is used in an amount of at least 0.01 percent of the mass of the molybdenum source;
3) the coordinated molybdenum oxide obtained in the step 2) is used as a raw material of the coating.
2. The method of preparing a solution processable high conductivity molybdenum oxide coating without annealing as claimed in claim 1, wherein:
in the step 1), the ratio of the molybdenum oxide to the hydrogen peroxide solution is as follows: 40-80 mg of molybdenum oxide and m l mg of hydrogen peroxide solution.
3. The method for preparing a solution processable high conductivity molybdenum oxide coating without annealing according to claim 1 or 2, wherein:
in the step 3), the coordinated molybdenum oxide solution obtained in the step 2) is dried to remove the solvent and then is dispersed in an organic solvent, and the dispersed product is a high-conductivity molybdenum oxide coating.
4. The method of preparing a solution processable high conductivity molybdenum oxide coating without annealing as claimed in claim 3, wherein:
the organic solvent is selected from one or more of isopropanol, methanol, ethanol, butanol, toluene, N-N-dimethyl sulfoxide and ethylene glycol methyl ether.
5. A method for preparing a film by using the coating obtained by the preparation method of any one of claims 1 to 4 as a raw material, which is characterized by comprising the following steps: dispersing the coating raw materials in an organic solvent to prepare a dispersion liquid, and preparing the molybdenum oxide film by a wet preparation process.
6. The method for producing a film according to claim 5, wherein:
the wet preparation process at least comprises one of the following steps: spin coating, doctor blading, screen printing, slot coating, spray coating, ink jet printing or wire rod printing.
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| CN102303908A (en) * | 2011-08-19 | 2012-01-04 | 西北有色金属研究院 | Method for preparing high-solubility industrial molybdenum oxide |
| CN104716262A (en) * | 2013-12-13 | 2015-06-17 | 中国科学院大连化学物理研究所 | Organic solar cell with ultra-thin nanosheets film as interlayers |
| CN106206953A (en) * | 2016-07-28 | 2016-12-07 | 桂林电子科技大学 | A kind of alcohol-soluble molybdenum oxide interlayer materials synthetic method and application |
| CN108054283A (en) * | 2017-12-14 | 2018-05-18 | 中国科学院化学研究所 | A kind of insensitive molybdenum trioxide anode interface layer of film thickness and preparation method thereof and the application in organic solar batteries |
| CN108539023A (en) * | 2018-04-11 | 2018-09-14 | 北京大学 | Ca-Ti ore type solar cell and preparation method thereof based on connection boron compound modification |
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| CN102303908A (en) * | 2011-08-19 | 2012-01-04 | 西北有色金属研究院 | Method for preparing high-solubility industrial molybdenum oxide |
| CN104716262A (en) * | 2013-12-13 | 2015-06-17 | 中国科学院大连化学物理研究所 | Organic solar cell with ultra-thin nanosheets film as interlayers |
| CN106206953A (en) * | 2016-07-28 | 2016-12-07 | 桂林电子科技大学 | A kind of alcohol-soluble molybdenum oxide interlayer materials synthetic method and application |
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