CN1645632A - Solid dye sensitized nanometer crystal solar battery and production thereof - Google Patents
Solid dye sensitized nanometer crystal solar battery and production thereof Download PDFInfo
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- CN1645632A CN1645632A CNA2005100235328A CN200510023532A CN1645632A CN 1645632 A CN1645632 A CN 1645632A CN A2005100235328 A CNA2005100235328 A CN A2005100235328A CN 200510023532 A CN200510023532 A CN 200510023532A CN 1645632 A CN1645632 A CN 1645632A
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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
- Y02E10/542—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
- 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
Abstract
The invention assembles a solid electrolyte at surface of nano-crystal formed by interaction of hydrogen bond between ion liquid and inorganic nano particles as electrolyte material. At the surface of wide-gap semiconductor adsorbing photosensitizer, a solid electrolyte is assembled to replace the liquid electrolyte. It can extend working life of solar cell.
Description
Technical field
The invention belongs to technical field of solar batteries, be specially a kind of dye sensitized nano crystal salar battery that utilizes the interaction of hydrogen bond formation between ionic liquid and the inorganic nano-particle and preparation method thereof.Surface-assembled solid electrolyte at the wide bandgap semiconductor nanometer crystal film that adsorbs photosensitizer replaces conventional liquid electrolyte, under the prerequisite of the electricity conversion of not obvious reduction solar cell, can prolong the useful life of solar cell significantly.
Background technology
Along with the develop rapidly of modern science and technology, energy and environment have become 21 century and have pressed for one of key issue of solution.Solar energy is inexhaustible green resource, is the optimal path that addresses this problem, so countries in the world competitively carry out the research that how to utilize solar energy one after another, and wherein solar cell is one of wherein important branch.The application of solar cell at present mainly concentrates on the monocrystalline silicon and the non-silicon solar cell of based semiconductor photovoltaic effect, though its photoelectric conversion efficiency height, complex process, cost an arm and a leg, the material requirements harshness, thereby be difficult to popularize.Nineteen nineties, Michael Gr professor tzel of Lausanne, SUI university has worked out dye sensitized nano crystal salar battery (referring to International Patent Application WO 91/16719), this dye sensitized nano crystal salar battery can overcome the shortcoming of silicon solar cell, have advantages such as manufacture craft is simple, material purity is less demanding, cheap, become the research focus in this field.
It is work electrode that dye sensitized nano crystal salar battery adopts the nanometer crystal film of the wide bandgap semiconductor of surface adsorption sensitising agent, because nanometer crystal film has very large specific area, can adsorb a large amount of sensitising agents, thereby can effectively absorb sunlight.The operation principle of dye sensitized nano crystal salar battery: when dyestuff absorbs sunlight, electronics is from the ground state transition to excitation state, the electronics of excitation state is transferred to rapidly in the semi-conductive conduction band, and the hole is stayed in the dyestuff, electronics is transferred to electrode through external circuit with after the Nano semiconductor network diffuses to conductive substrates, and the dyestuff of oxidation state is reduced the electrolyte reduction of attitude, the electrolyte of oxidation state is reduced in that electrode is accepted electronics, thereby finishes the transportation of electronics.
At present, the electrolyte of dye sensitized nano crystal salar battery mainly adopts and contains I
3 -/ I
2The acetonitrile solution of oxidation-reduction pair, but there is the problem of solvent evaporates and leakage in liquid electrolyte.In order to overcome these shortcomings, develop into the quasi-solid electrolyte that contains some gelatinizing agents gradually, improved the stability of battery to a certain extent.
In order thoroughly to solve the stability of solar cell, all solid state electrolyte is best selection.Solid electrolyte mainly adopts P-type inorganic semiconductor, organic hole transferring material at present, but the electronics of all solid state electrolyte and ionic conductivity sharply descend, effect is unsatisfactory, therefore, the efficient that how to improve the dye sensitized nano crystal salar battery of solid electrolyte becomes the important development direction of dye sensitized nano crystal salar battery.
Summary of the invention
The object of the present invention is to provide a kind of solid-state dye sensitized nano crystal salar battery and preparation method thereof, make this solar cell under the prerequisite of the electricity conversion of not obvious reduction battery, can prolong the useful life of solar cell significantly.
The solid-state dye sensitized nano crystal salar battery that the present invention proposes, the surface-assembled solid electrolyte of the wide bandgap semiconductor nanometer crystal film of photosensitizer has been adsorbed in employing, as electrolyte, replace conventional liquid electrolyte, its two sides is the electro-conductive glass that is coated with platinum layer, forms sandwich shape, and encapsulates composition with paraffin, wherein the dye sensitized nano crystal film is a work electrode, and the electro-conductive glass of platinum plating layer is to electrode.Its structure as shown in Figure 1.
Among the present invention, described solid electrolyte is to utilize the interaction of hydrogen bond between ionic liquid and the inorganic nano-particle to form.Wherein, inorganic nano-particle is selected from Al
2O
3, SiO
2, TiO
2,, ZrO
2, the ZnO oxide, ionic liquid is selected from 1, the perchlorate of 3-dialkylimidazolium salt, nitrate, salt compounded of iodine, villaumite, bromine salt, tetrafluoroborate, hexafluorophosphate, three fluoro sulfonates, acetate etc., wherein, imidazolidinyl is selected from methyl, ethyl until octadecyl.
Wide bandgap semiconductor nanometer crystal film of the present invention adopts the titanium dioxide nanocrystalline film, photosensitizer adopts cis-two thiocyanate radical-two (4,4 '-dicarboxylic acids-2,2 ' bipyridine) closes ruthenium cis-dithiocyanato bis (4,4 ' dicarboxy-2,2 '-bipyridine) ruthenium (being called for short the N3 dyestuff) or cis-two thiocyanate radical-4,4 '-dicarboxylic acids-2,2 ' bipyridine-4,4 '-dinonyl-2,2 ' bipyridine closes ruthenium cis-dithiocyanato4,4 '-dicarboxy-2,2 '-bipyridine-4,4 '-dinonyl-2,2 '-bipyridineruthenium (being called for short the Z907 dyestuff).
Above-mentioned electro-conductive glass can adopt the tin ash electro-conductive glass of mixing fluorine.
The preparation method of dye sensitized nano crystal salar battery of the present invention, it is characterized in that on the surface of the wide bandgap semiconductor nanometer crystal film that passes through dye sensitization, assembling solid electrolyte, electro-conductive glass with platinum plating is placed on the semiconductor nano epitaxial of dye sensitization then, promptly constitute the sandwich type dye sensitized nano crystal salar battery, and encapsulate with heat-seal adhesive.
In the said method, the wide bandgap semiconductor nanometer crystal film adopts nano titanium dioxide film.
The preparation method of semiconductor nano epitaxial is as follows in the said method: with granularity is that the colloidal tio 2 of 10-100 nanometer is coated on and forms broad stopband nano titanium oxide epitaxial on the transparent conductive substrate, 200-600 ℃ of following roasting 15 minutes to 12 hours, cooling back repetitive operation was until the broad stopband nano titanium oxide epitaxial that obtains the 1-50 micron.Wherein transparent conductive substrate adopts the tin ash electro-conductive glass of mixing fluorine.
In the said method, dye sensitization is as follows: broad stopband nano titanium oxide epitaxial is put into baking oven heated 10-120 minute down in 100-250 ℃, being immersed in concentration when being cooled to 25-100 ℃ is 10
-5-10
-3Sensitization in 2-48 hour in the N3 of mol or the Z907 dyestuff.
In the said method, the step of assembling solid electrolyte is as follows: the electrolyte constituent is dissolved into 1 respectively, and in the 3-dialkylimidazolium salt, its concentration is respectively: I
2Concentration be the 0.05-0.5 mol, the concentration of 1-methyl-3-propyl imidazole salt compounded of iodine is the 0.1-2.0 mol, the concentration of 4-tert .-butylpyridine is the 0.1-1.0 mol, to be mixed evenly after, the nano-oxide that adds given content, electrolyte solidifies rapidly, and wherein the mass content of nano-oxide in solid electrolyte is 1-10%.
In the said method, described 1, the anion of 3-dialkylimidazolium salt is selected from a kind of of perchlorate, nitrate, salt compounded of iodine, villaumite, bromine salt, tetrafluoroborate, hexafluorophosphate, three fluoro sulfonates etc., imidazolidinyl wherein is methyl, ethyl until octadecyl etc., and nano-oxide is selected from Al
2O
3, SiO
2, TiO
2,, ZrO
2, oxide such as ZnO.
The Optical Electro-Chemistry of dye sensitized nano crystal salar battery of the present invention is measured according to traditional three-electrode system and is measured, radiation source is five grades of adjustable 500W xenon lamp (Ushio Electric, Japan) or 1000W solar simulator (1.5AM) (Oriel, USA).Photoelectric current and photovoltage output are measured by Keithley2400 digital source table (U.S. Keithley company).
The present invention mainly utilizes the interaction of hydrogen bond between ionic liquid and the inorganic nano-particle to form the dye sensitized nano crystal salar battery solid electrolyte, under the prerequisite of not obvious reduction cell photoelectric conversion efficiency, prolong the useful life of dye sensitized nano crystal salar battery significantly.For example, compare with liquid electrolyte, be 4.7%, 1000 hour based on the photoelectric conversion efficiency of the dye sensitized nano crystal salar battery of interaction of hydrogen bond after, electricity conversion still is original more than 90%, and only is original 30% based on the photoelectric conversion efficiency of liquid electrolyte.
Description of drawings
Fig. 1 dye sensitized nano crystal salar battery structural representation of the present invention
The photoelectric current of the dye sensitized nano crystal salar battery of Fig. 2 liquid electrolyte-photovoltage curve
Fig. 3 is based on the photoelectric current-photovoltage curve of the dye sensitized nano crystal salar battery of the solid electrolyte of 1% nano silicon
Fig. 4 is based on the photoelectric current-photovoltage curve of the dye sensitized nano crystal salar battery of the solid electrolyte of 3% nano silicon
Fig. 5 is based on the photoelectric current-photovoltage curve of the dye sensitized nano crystal salar battery of the solid electrolyte of 10% nano silicon
Fig. 6 is based on the photoelectric current-photovoltage curve of the dye sensitized nano crystal salar battery of the solid electrolyte of 2% nano titanium oxide
Fig. 7 is based on the photoelectric current-photovoltage curve of the dye sensitized nano crystal salar battery of the solid electrolyte of 4% nano zine oxide
Fig. 8 is based on the dye sensitized nano crystal salar battery of the solid electrolyte of 3% the nano silicon photoelectric current-photovoltage curve at 40 ℃
Fig. 9 is based on the dye sensitized nano crystal salar battery of the solid electrolyte of 3% the nano silicon photoelectric current-photovoltage curve at 60 ℃
The stability of the normalized dye sensitized nano crystal salar battery based on liquid electrolyte of Figure 10.
The normalized stability of Figure 11 based on the dye sensitized nano crystal salar battery that contains 5% nano silicon solid electrolyte
Embodiment
Embodiment 1: with a titanium dioxide nanocrystalline membrane electrode 5 * 10
-4Soak sensitization in 24 hours in the ethanolic solution of mol N3 dyestuff.Drip 0.1 milliliter and contain 0.1 mol I
2, 0.5 mol 4-tert .-butylpyridine, 1 mol 1-methyl-3-propyl group-iodonium imidazolide salts, then the ito glass of a slice platinum plating is placed on dye sensitization the nano titanium oxide epitaxial on, measure with clamp.At 100mW/cm
2White light under record open circuit photovoltage 628.17mV, the short-circuit photocurrent 4.62mA/cm of electrode
2, fill factor, curve factor 0.59, energy conversion efficiency 2.3%.
Embodiment 2: with a titanium dioxide nanocrystalline membrane electrode 5 * 10
-4Soak sensitization in 24 hours in the ethanolic solution of mol N3 dyestuff.Drip 0.1 milliliter and contain 0.05 mol I
20.5 mol 4-tert .-butylpyridine, 2.0 mol 1-methyl-3-propyl group-iodonium imidazolide salts, the 1-methyl of 1% nano silicon-3-propyl group-imidazoles hexafluorophosphate solid electrolyte, then the ito glass of a slice platinum plating is placed on dye sensitization the nano titanium oxide epitaxial on, measure with clamp.At 100mW/cm
2White light under record open circuit photovoltage 660.03mV, the short-circuit photocurrent 5.92mA/cm of electrode
2, fill factor, curve factor 0.56, energy conversion efficiency 2.9%.
Embodiment 3: with a titanium dioxide nanocrystalline membrane electrode 5 * 10
-4Soak sensitization in 48 hours in the ethanolic solution of mol N3 dyestuff.Drip 0.1 milliliter and contain 0.5 mol I
20.5 mol 4-tert .-butylpyridine, 1 mol 1-methyl-3-propyl group-iodonium imidazolide salts, the 1-methyl of 3% nano silicon-3-hexyl-imidazoles three fluoro sulfonate solid electrolytes, then the ito glass of a slice platinum plating is placed on dye sensitization the nano titanium oxide epitaxial on, measure with clamp.At 100mW/cm
2White light under record open circuit photovoltage 616.12mV, the short-circuit photocurrent 7.84mA/cm of electrode
2, fill factor, curve factor 0.59, energy conversion efficiency 3.8%.
Embodiment 4: with a titanium dioxide nanocrystalline membrane electrode 5 * 10
-4Soak sensitization in 24 hours in the ethanolic solution of mol N3 dyestuff.Drip 0.1 milliliter and contain 0.1 mol I
21.0 mol 4-tert .-butylpyridine, 1 mol 1-methyl-3-propyl group-iodonium imidazolide salts, the 1-methyl of 10% nano silicon-3-octadecyl-imidazoles hexafluorophosphate solid electrolyte, then the ito glass of a slice platinum plating is placed on dye sensitization the nano titanium oxide epitaxial on, measure with clamp.At 100mW/cm
2White light under record open circuit photovoltage 654.88mV, the short-circuit photocurrent 8.02mA/cm of electrode
2, fill factor, curve factor 0.67, energy conversion efficiency 4.7%.
Embodiment 5: with a titanium dioxide nanocrystalline membrane electrode 5 * 10
-4Soak sensitization in 3 hours in the ethanolic solution of mol Z907 dyestuff.Drip 0.1 milliliter and contain 0.1 mol I
20.1 mol 4-tert .-butylpyridine, 1 mol 1-methyl-3-propyl group-iodonium imidazolide salts, the 1-methyl of 2% nano titanium oxide-3-propyl group-imidazole nitrate solid electrolyte, then the ito glass of a slice platinum plating is placed on dye sensitization the nano titanium oxide epitaxial on, measure with clamp.At 100mW/cm
2White light under record open circuit photovoltage 660.0mV, the short-circuit photocurrent 6.03mA/cm of electrode
2, fill factor, curve factor 0.57, energy conversion efficiency 3.0%.
Embodiment 6: with a titanium dioxide nanocrystalline membrane electrode 5 * 10
-4Soak sensitization in 24 hours in the ethanolic solution of mol Z907 dyestuff.Drip 0.1 milliliter and contain 0.1 mol I
20.5 mol 4-tert .-butylpyridine, 1 mol 1-methyl-3-propyl group-iodonium imidazolide salts, the 1-methyl of 4% nano aluminium oxide-3-propyl group-tetrafluoroborate solid electrolyte, then the ito glass of a slice platinum plating is placed on dye sensitization the nano titanium oxide epitaxial on, measure with clamp.At 100mW/cm
2White light under record open circuit photovoltage 620.7mV, the short-circuit photocurrent 5.91mA/cm of electrode
2, fill factor, curve factor 0.62, energy conversion efficiency 3.02%.
Embodiment 7: with a titanium dioxide nanocrystalline membrane electrode 5 * 10
-4Soak sensitization in 24 hours in the ethanolic solution of mol Z907 dyestuff.Drip 0.1 milliliter and contain 0.1 mol I
20.5 mol 4-tert .-butylpyridine, 1 mol 1-methyl-3-propyl group-iodonium imidazolide salts, the 1-methyl of 3% nano zine oxide-3-propyl group-tetrafluoroborate solid electrolyte, then the ito glass of a slice platinum plating is placed on dye sensitization the nano titanium oxide epitaxial on, measure with clamp.At 100mW/cm
2White light under record open circuit photovoltage 559.02mV, the short-circuit photocurrent 8.43mA/cm of electrode
2, fill factor, curve factor 0.59, energy conversion efficiency 3.75%.
Embodiment 8: with a titanium dioxide nanocrystalline membrane electrode 5 * 10
-4Soak sensitization in 24 hours in the ethanolic solution of mol N3 dyestuff.Drip 0.1 milliliter and contain 0.1 mol I
20.5 mol 4-tert .-butylpyridine, 1 mol 1-methyl-3-propyl group-iodonium imidazolide salts, the 1-methyl of 3% nano silicon-3-propyl group-tetrafluoroborate solid electrolyte, then the ito glass of a slice platinum plating is placed on dye sensitization the nano titanium oxide epitaxial on, measure with clamp.At 100mW/cm
2White light under, 40 ℃ of open circuit photovoltage 559.02mV, short-circuit photocurrent 8.43mA/cm that record electrode
2, fill factor, curve factor 0.59, energy conversion efficiency 3.75%.
Embodiment 9: with a titanium dioxide nanocrystalline membrane electrode 5 * 10
-4Soak sensitization in 24 hours in the ethanolic solution of mol N3 dyestuff.Drip 0.1 milliliter and contain 0.1 mol I
20.5 mol 4-tert .-butylpyridine, 1 mol 1-methyl-3-propyl group-iodonium imidazolide salts, the 1-methyl of 3% nano silicon-3-propyl group-imidazoles villaumite solid electrolyte, then the ito glass of a slice platinum plating is placed on dye sensitization the nano titanium oxide epitaxial on, measure with clamp.At 100mW/cm
2White light under, 60 ℃ of open circuit photovoltage 584.15mV, short-circuit photocurrent 8.33mA/cm that record electrode
2, fill factor, curve factor 0.58, energy conversion efficiency 3.78%.
Claims (9)
1, a kind of dye sensitized nano crystal salar battery, it is characterized in that adopting the solid electrolyte on the surface-assembled of wide bandgap semiconductor nanometer crystal film of absorption photosensitizer is electrolyte, its two sides is the electro-conductive glass that is coated with platinum layer, form sandwich shape, wherein the dye sensitized nano crystal film is a work electrode, and the electro-conductive glass of platinum plating layer is to electrode.
2, dye sensitized nano crystal salar battery according to claim 1 is characterized in that the wide bandgap semiconductor nanometer crystal film is the titanium dioxide nanocrystalline film.
3,, it is characterized in that said photosensitizer is N3 or Z907 dyestuff according to claim 1 or 2 described dye sensitized nano crystal salar batteries.
4, dye sensitized nano crystal salar battery according to claim 1 is characterized in that said solid electrolyte material is to utilize the interaction of hydrogen bond between ionic liquid and the inorganic nano-particle to form.
5, dye sensitized nano crystal salar battery according to claim 4 is characterized in that said inorganic nano-particle is selected from Al
2O
3, SiO
2, TiO
2,, ZrO
2, the ZnO oxide, ionic liquid is selected from 1, the perchlorate of 3-dialkylimidazolium salt, nitrate, salt compounded of iodine, villaumite, bromine salt, tetrafluoroborate, hexafluorophosphate, three fluoro sulfonates, acetate etc., wherein, imidazolidinyl is selected from methyl, ethyl until octadecyl.
6, a kind of preparation method as one of claim 1-5 described dye sensitized nano crystal salar battery, it is characterized in that on the surface of the wide bandgap semiconductor nanometer crystal film that passes through dye sensitization, assembling solid electrolyte, electro-conductive glass with platinum plating is placed on the semiconductor nano epitaxial of dye sensitization then, use clamp, promptly constitute the sandwich type dye sensitized nano crystal salar battery, and encapsulate with heat-seal adhesive.
7, the preparation method of dye sensitized nano crystal salar battery according to claim 6, the step that it is characterized in that assembling solid electrolyte is as follows: the electrolyte constituent is dissolved into 1 respectively, in the perchlorate of 3-dialkylimidazolium, nitrate, salt compounded of iodine, villaumite, bromine salt, tetrafluoroborate, hexafluorophosphate, three fluoro sulfonates or the acetate, its concentration is respectively: I
2Concentration be the 0.05-0.5 mol, the concentration of 1-methyl-3-propyl imidazole salt compounded of iodine is the 0.1-2.0 mol, the concentration of 4-tert .-butylpyridine is the 0.1-1.0 mol, to be mixed evenly after, add nano-oxide, electrolyte solidifies rapidly, and wherein the nano-oxide addition is the 1-10% of electrolyte quality.
8, the preparation method of dye sensitized nano crystal salar battery according to claim 6, the preparation method who it is characterized in that the semiconductor nano epitaxial is as follows: with granularity is that the colloidal tio 2 of 1-50 nanometer is coated on and forms broad stopband nano titanium oxide epitaxial on the transparent conductive substrate, 200-600 ℃ of following roasting 15 minutes to 12 hours, cooling back repetitive operation was until the broad stopband nano titanium oxide epitaxial that obtains the 1-50 micron.
9, the preparation method of dye sensitized nano crystal salar battery according to claim 6, the sensitization step that it is characterized in that nanometer crystal film is: broad stopband nano titanium oxide epitaxial is put into baking oven heated 10-120 minute down in 100-250 ℃, being immersed in concentration when being cooled to 25-100 ℃ is 10
-5-10
-3Sensitization in 2-48 hour in the N3 of mol or the Z907 dyestuff.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101789317A (en) * | 2010-03-12 | 2010-07-28 | 华中科技大学 | Dye sensitization solar battery and preparation method thereof |
| CN101740224B (en) * | 2009-12-25 | 2012-03-28 | 彩虹集团公司 | Preparation method of dye-sensitized solar battery forming ionic liquid crystallizing system |
| CN102136374B (en) * | 2010-01-21 | 2013-07-10 | 财团法人工业技术研究院 | Dye sensitized solar cell and preparation method thereof |
| WO2020083394A1 (en) * | 2018-10-25 | 2020-04-30 | 纳晶科技股份有限公司 | Electroluminescent device, preparation method therefor, and nanocrystalline ink |
-
2005
- 2005-01-24 CN CNA2005100235328A patent/CN1645632A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101740224B (en) * | 2009-12-25 | 2012-03-28 | 彩虹集团公司 | Preparation method of dye-sensitized solar battery forming ionic liquid crystallizing system |
| CN102136374B (en) * | 2010-01-21 | 2013-07-10 | 财团法人工业技术研究院 | Dye sensitized solar cell and preparation method thereof |
| CN101789317A (en) * | 2010-03-12 | 2010-07-28 | 华中科技大学 | Dye sensitization solar battery and preparation method thereof |
| WO2020083394A1 (en) * | 2018-10-25 | 2020-04-30 | 纳晶科技股份有限公司 | Electroluminescent device, preparation method therefor, and nanocrystalline ink |
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