CN101834069A - Method for sensitizing semi-conductor double membrane by dye - Google Patents
Method for sensitizing semi-conductor double membrane by dye Download PDFInfo
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- CN101834069A CN101834069A CN201010139901A CN201010139901A CN101834069A CN 101834069 A CN101834069 A CN 101834069A CN 201010139901 A CN201010139901 A CN 201010139901A CN 201010139901 A CN201010139901 A CN 201010139901A CN 101834069 A CN101834069 A CN 101834069A
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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
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/542—Dye sensitized solar cells
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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
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
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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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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Abstract
The invention discloses a method for sensitizing a semi-conductor double membrane by a dye, which mainly comprises the following steps of: making membrane surfaces of two semi-conductor membranes opposite and clamping the two semi-conductor membranes by using a fixture to form a double membrane, wherein the gap of the two membranes is between 0.01 and 0.50mm; immersing the lower end of the double membrane into photosensitive dye solution at the concentration of 10<-7>-10<-3>mol/L, and making the main body positioned above the liquid level, and making the dye solution filled in the gap of the double membrane through capillary action at the temperature of between 10 and 90 DEG C for 10 to 30 hours; and taking the semi-conductor membranes out, washing off residual dye solution adsorbed on the membrane surfaces by using a cleaning agent, and drying and storing. The method has the advantages of effectively controlling the dye sensitization degree and making the dye sensitization uniform, along with high dye utilization rate, light pollution, low cost and easy industrialization.
Description
Technical field the present invention relates to a kind of manufacture method of dye-sensitized semiconductor material.
The background technology solar cell is a kind of green regenerative energy sources of tool potentiality to be exploited.Commercial at present silicon solar cell, because problems such as its manufacturing process complexity, cost costliness, photoetch and industrial monocrystalline silicon reserves, extensive prolonged application faces difficulty.1991, Switzerland scientist M.Gratzel professor, developed a kind of brand new solar energy battery---dye-sensitized nano solar cell (dye-sensitized solarcell, DSSC also claim " Gratzel cell ").This battery is not subjected to the restriction of natural resources, manufacture method simple, cost only is 1/5～1/10 of a silicon solar cell, has very big DEVELOPMENT PROSPECT, its key has been to use the good dye-sensitized nano titanium dioxide semiconductor light anode of very cheap performance, this anode is made of the metal-oxide film of transparent substrate, conductive layer and load light-sensitive coloring agent, and this semiconductor that is loaded with dyestuff is called the dye-sensitized semiconductor electrode.But the method difference of dye-sensitized semiconductor film preparation dyestuff semiconductor composite electrode, the dye-sensitized semiconductor material that obtains can be in photoelectric properties-cost of manufacture-process difference to some extent in the environmental protection, directly influenced operating efficiency--the cost and the technology green degree environmental protection cost of battery.Up to the present, the method of dye-sensitized semiconductor material mainly is that dyestuff is made into certain solution, then by method for sensitizing (application numbers of related application following 200710170393 such as dipping, printing, spraying, blade coating, spin coating, spraying thermal decompositions, 200780011820,200910303700.7,200910041296.3,200910088194.4) and make dyestuff compound with physics and/or chemical bonding mode and semiconductor.Infusion process does not wherein generally relate to use and a large amount of solvent evaporates pollution problem of specialized equipment, compare with other method, it is the most energy-conservation easy a kind of dye-sensitized semiconductor method (application number of related application following 200910055090.3 that in dye-sensitized solar cell anode is made, is widely used, 200910160045.4,200910023103.9,200910052884.4,200910111911.0,200910131154.3 etc.).But this method realizes sensitization by semiconductor membrane being immersed in fully in the dye solution (several hours to tens hours), the concentration of dye solution changes in activation process, the change of concentration can cause the inhomogeneities of dye sensitization, and the low concentration dye solution of remainder after the sensitization, reuse rate variance, the Chang Zuowei discharging of waste liquid falls, and so not only the utilance of dyestuff is low, wasted a large amount of dyestuffs, cost is improved; And wayward monolayer dye sensitization, multilayer sensitization meeting makes the transmission of internal layer dyestuff obstruction electronics, reduces the opto-electronic conversion performance of material; Also can pollute environment in addition.
Summary of the invention the object of the invention is to provide a kind of can not only effectively control the dye sensitization degree, dye sensitization is even, and dye utilization rate height, pollution is little, cost is low method for sensitizing semi-conductor double membrane by dye.The present invention mainly is: the face of two on-chip semiconductive thin films is relative, and the bottom is immersed under the dyestuff liquid level, utilizes capillarity that dye solution is evenly entered and is full of slit between two faces, makes the face of semiconductive thin film carry out dye sensitization.
Specific practice of the present invention is:
(1) preparation of dye solution:
1. dyestuff that can the sensitized semiconductor film has a lot, and sensitizing dyestuff of the present invention can be the homogencous dyes component, also can be the compound of multiple dye component.These dyestuffs can be Bipyridine metal complexes class dyestuff, organic molecule dyestuff, high molecular dye, phthalocyanine, cyanine dyes, spiro-pyrans, triaryl methane type, porphyrin class, thiazide, naphthalenetetracarbacidic acidic acid anhydride Lei He 3,4, 9, 10-perylenetetracarboxylic dianhydride class etc.
2. above-mentioned sensitizing dyestuff is dissolved in the solvent with its adaptation, is made into certain density solution, it is fixed that the selection of concrete concentration can be come by the character of semiconductor and dyestuff and desired sensitization, generally 10
-7-10
-3Between the mol/L.Solvent can be methyl alcohol, ethanol, N, the mixed solvent of dinethylformamide, acetone, toluene, dimethylbenzene, chloroform, water, acetonitrile or their compositions etc.
(2) dyestuff and semiconductor membrane is compound:
1. treat the promptly surperficial substrate of semiconductor membrane of sensitization with semiconductive thin film; this substrate can be glass, pottery, metal or the high molecular polymer with conductive features, and this high molecular polymer can be PETG, polyimides, PEN, Merlon, polypropylene, tri acetyl cellulose, polyether sulfone or their composition.Above-mentioned substrate can be any or several conducting metals or metallic compound such as tin indium oxide (ITO), fluorine oxide tin (FTO), ZnO-(Ga2O3 or Al2O3) tin-based oxide, antimony tin (ATO) and combination thereof.
Above-mentioned semiconductive thin film can be any one-component or the compound semiconductive thin film of various ingredients with characteristic of semiconductor, also comprises the oxide or the sulfide of at least a metal of selecting in the following material, i.e. Ti, Zr, Sr, Zn, In, Yr, La, V, Mo, W, Sn, Nb, Mg, Al, Y, Sc, Ga or their composition also comprise and add the composite semiconductor films that other materials form in every way in them.
2. relatively also (also can be with the face of above-mentioned two chip semiconductor diaphragms with the relative clamp of also using of above-mentioned a slice semiconductor membrane with other substrate with clamp, a slice semiconductor membrane is carried out sensitization), both constitute two diaphragms, two diaphragm gaps are generally between 0.01-0.50mm, to guarantee forming capillarity, dye solution is risen automatically equably be full of the gap.
3. the lower end of above-mentioned pair of diaphragm is immersed under the above-mentioned dye solution liquid level for preparing, and main part is positioned on the liquid level.Dye solution is evenly entered and be full of slit between two faces by capillarity, kept 10-30 hour down, make semiconductor two faces finish sensitization at 10-90 ℃.
4. take out semiconductor membrane, wash the excess dyestuff liquid that is attached on the film surface off with irrigation after, drying promptly gets the dye-sensitized semiconductor material, can be in kept dry under the vacuum.
The present invention compared with prior art has following advantage:
1, makes dye solution evenly be full of slit between two faces by capillarity, make semiconductor two faces carry out dye sensitization, so the dyestuff consumption is few, and sensitization is effective.
2, the dyes concentration of the lower end of two diaphragms immersion remains unchanged substantially, and is reusable.The raising of quality and utilance, cost reduced when dyestuff was recycled; The 2nd, avoided the formation of a large amount of dyestuff waste liquids and the volatilization of solvent, be beneficial to energy-saving and emission-reduction and environmental protection.
3, dye sensitization simple in equipment does not need special special electrodynamic instrument, and is easy and simple to handle, is easy to industrial applications.
4, the preparation of this method dye-sensitized semiconductor film composite material of being suitable for using in every field also comprises fields such as solar cell, manual simulation's photosynthesis, photocatalysis, photodissociation hydrogen manufacturing and light degradation.
Description of drawings
Fig. 1 is a simplified schematic diagram of the present invention.
Fig. 2 is the structural formula of linearity three methine cyanine dyes used in the embodiment of the invention 2.
Fig. 3 is the structural formula of squarylium cyanine dyes used in the embodiment of the invention 3.
Fig. 4 is the structural formula of the chloride hexa-atomic bridged ring indole cyanine dyes of meta used in the embodiment of the invention 4.
Embodiment
In dye-sensitized semiconductor dual-diaphragm work schematic diagram shown in Figure 1, the container 1 of splendid attire dye solution is equipped with the semiconductor membrane for the treatment of sensitization that is covered with semiconductive thin film 3 on the substrate 2, its two face relatively and top by clamp, the lower end is immersed under the dye solution liquid level for preparing, and main part is positioned on the liquid level.
Embodiment 1
Two semiconductor faces with nano titanium oxide semiconductor film conductive glass sheet for the treatment of sensitization are constituted two diaphragms relatively and use clamp, and two diaphragm gap widths are about 0.08mm.It is 10 that the concentration for preparing is in advance immersed in the lower end of above-mentioned pair of diaphragm
-4Under the mol/L rhodamine B light-sensitive coloring agent methanol solution liquid level, and main part is positioned on the liquid level.Make dye solution be full of the gap of two diaphragms by capillarity, 45 ℃ kept after 15 hours, take out semiconductor membrane, after rinsing out the excess dyestuff liquid that is attached on the film surface with absolute methanol, lucifuge, dry under the vacuum, preserve, promptly obtain the nano titanium oxide semiconductive thin film conductive glass electrode material of rhodamine B dye sensitization.
Embodiment 2
Two semiconductor faces with nano silicon semiconductor film conductive glass sheet for the treatment of sensitization are constituted two diaphragms relatively and use clamp, and two diaphragm gap widths are about 0.4mm.It is 10 that the concentration for preparing is in advance immersed in the lower end of above-mentioned pair of diaphragm
-7Linear three methine cyanine dyes (structural formula is seen Fig. 2) and the N of mol/L light-sensitive coloring agent, under the liquid level of solution that dinethylformamide and n-butanol are mixed with, and main part is positioned on the liquid level.Make dye solution be full of the gap of two diaphragms by capillarity, 80 ℃ keep taking out diaphragm after 12 hours, fall to be attached to excess dyestuff liquid on the film surface with washed with methanol after, kept dry promptly obtains the cyanine dye-sensitized nano silicon thin-film material of linear three methines.
Embodiment 3
Two semiconductor faces with nano titanium oxide semiconductive thin film conductivity ceramics sheet for the treatment of sensitization are relatively also used clamp, and two diaphragm gap widths are about 0.1mm.It is 10 that the concentration for preparing is in advance immersed in the lower end of above-mentioned pair of diaphragm
-6Under the liquid level of solution that mol/L squarylium cyanine dyes (structural formula is seen Fig. 3) light-sensitive coloring agent and acetonitrile and methyl alcohol are mixed with, and main part is positioned on the liquid level.Make dye solution be full of the gap of two diaphragms by capillarity, 25 ℃ of lucifuges kept after 16 hours, take out semiconductor membrane, after rinsing out the excess dyestuff liquid that is attached on the film surface with absolute methanol, lucifuge, kept dry promptly obtains the nano titanium oxide semiconductor film material of squarylium cyanine dyes sensitization.
Embodiment 4
Two semiconductor faces with nano titanium oxide semiconductor film conductive glass sheet for the treatment of sensitization are constituted two diaphragms relatively and use clamp, and two diaphragm gap widths are about 0.05mm.It is 10 that the concentration for preparing is in advance immersed in the lower end of above-mentioned pair of diaphragm
-3Under the liquid level of solution that chloride hexa-atomic bridged ring indole cyanine dyes (structural formula is seen Fig. 4) light-sensitive coloring agent of mol/L meta and chloroform and methyl alcohol are mixed with, and main part is positioned on the liquid level.Make dye solution be full of the gap of two diaphragms by capillarity, 10 ℃ of lucifuges kept after 28 hours, take out semiconductor membrane, after falling to be attached to excess dyestuff liquid on the film surface with washed with methanol, lucifuge, kept dry under the vacuum promptly obtains the nano titanium oxide semiconductive thin film conductive glass electrode material of the chloride hexa-atomic bridged ring indole cyanine dyes III of meta sensitization.
Embodiment 5
Two semiconductor faces with nano zine oxide semiconductive thin film conductive plastic film for the treatment of sensitization are constituted two diaphragms relatively and use clamp, and two diaphragm gap widths are about 0.2mm.It is 10 that the concentration for preparing is in advance immersed in the lower end of above-mentioned pair of diaphragm
-4Under the liquid level of solution that mol/L porphyrin light-sensitive coloring agent and ethanol are mixed with, and main part is positioned on the liquid level.Make dye solution be full of the gap of two diaphragms by capillarity, 35 ℃ keep taking out semiconductor membrane after 25 hours, after falling to be attached to excess dyestuff liquid on the film surface with alcohol flushing, lucifuge, kept dry under the vacuum promptly obtains the zinc oxide semiconductor thin film material of porphyrin light-sensitive coloring agent sensitization.
Embodiment 6
Two semiconductor faces with nano-stannic oxide semiconductor film conductive glass sheet for the treatment of sensitization are relatively also used clamp, and two diaphragm gap widths are about 0.03mm.It is 10 that the concentration for preparing is in advance immersed in the lower end of above-mentioned pair of diaphragm
-5Under the liquid level of solution that mol/L phthalocyanine dye and dimethylbenzene are mixed with, and main part is positioned on the liquid level.Make dye solution be full of the gap of two diaphragms by capillarity, 60 ℃ keep taking out semiconductor membrane after 24 hours, after falling to be attached to excess dyestuff liquid on the film surface with alcohol flushing, lucifuge, kept dry under the vacuum promptly obtains the tin ash semiconductor film material of phthalocyanine dye sensitization.
Claims (2)
1. method for sensitizing semi-conductor double membrane by dye is characterized in that: the face of two chip semiconductor diaphragms is constituted two diaphragms relatively and with clamp, and concentration 10 is immersed with the lower end of above-mentioned pair of diaphragm in two diaphragm gaps between 0.01-0.50mm
-7-10
-3Under the mol/L light-sensitive coloring agent liquid level of solution, and main part is positioned on the liquid level, make the automatic rising of dye solution be full of two diaphragm gaps by capillarity and carry out dye sensitization, process was taken out semiconductor membrane in 10-30 hour under 10-90 ℃, after washing the excess dyestuff liquid that is attached on the film surface off with irrigation, kept dry.
2. method for sensitizing semi-conductor double membrane by dye according to claim 1 is characterized in that: with the two diaphragms of the relative composition with other substrate of above-mentioned a slice semiconductor membrane, a slice semiconductor membrane is carried out sensitization.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN2010101399010A CN101834069B (en) | 2010-04-07 | 2010-04-07 | Method for sensitizing semi-conductor double membrane by dye |
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| CN2010101399010A CN101834069B (en) | 2010-04-07 | 2010-04-07 | Method for sensitizing semi-conductor double membrane by dye |
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| CN101834069B CN101834069B (en) | 2012-06-27 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111161958A (en) * | 2020-01-03 | 2020-05-15 | 南昌航空大学 | Method for preparing multilayer co-sensitized film by light control technology |
| CN111161956A (en) * | 2020-01-03 | 2020-05-15 | 南昌航空大学 | Method for preparing co-sensitization film by bidirectional diffusion technology |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1106716A (en) * | 1993-05-05 | 1995-08-16 | 哈马技术半导体机械制造及科技有限公司 | Apparatus for application of lacquer or film on board or circular plate |
| EP1020881A2 (en) * | 1999-01-14 | 2000-07-19 | Fuji Photo Film Co., Ltd. | Photo-electrochemical cell |
| EP1164603A2 (en) * | 2000-06-15 | 2001-12-19 | Fuji Photo Film Co., Ltd. | Dye sensitized solar cell |
| CN1534021A (en) * | 2003-04-02 | 2004-10-06 | �Ϻ���ͨ��ѧ | Large conjugated half cyanine dye, its synthesis and its sensitized nano-crystal semiconductor solar energy battery |
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- 2010-04-07 CN CN2010101399010A patent/CN101834069B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1106716A (en) * | 1993-05-05 | 1995-08-16 | 哈马技术半导体机械制造及科技有限公司 | Apparatus for application of lacquer or film on board or circular plate |
| EP1020881A2 (en) * | 1999-01-14 | 2000-07-19 | Fuji Photo Film Co., Ltd. | Photo-electrochemical cell |
| EP1164603A2 (en) * | 2000-06-15 | 2001-12-19 | Fuji Photo Film Co., Ltd. | Dye sensitized solar cell |
| CN1534021A (en) * | 2003-04-02 | 2004-10-06 | �Ϻ���ͨ��ѧ | Large conjugated half cyanine dye, its synthesis and its sensitized nano-crystal semiconductor solar energy battery |
Non-Patent Citations (1)
| Title |
|---|
| 《台湾博硕士论文知识加值系统》 20081231 黄婉敏 纳米CdSe、ZnO与TiO2之合成及分析与其应用于敏化太阳能电池研究 50页3.3.6 1、2 , 2 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111161958A (en) * | 2020-01-03 | 2020-05-15 | 南昌航空大学 | Method for preparing multilayer co-sensitized film by light control technology |
| CN111161956A (en) * | 2020-01-03 | 2020-05-15 | 南昌航空大学 | Method for preparing co-sensitization film by bidirectional diffusion technology |
| CN111161956B (en) * | 2020-01-03 | 2021-06-22 | 南昌航空大学 | Method for preparing co-sensitization film by bidirectional diffusion technology |
| CN111161958B (en) * | 2020-01-03 | 2021-06-22 | 南昌航空大学 | Method for preparing multilayer co-sensitized film by light control technology |
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