CN102674335A - Method for preparing graphene based on free radical reaction at low temperature - Google Patents
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- CN102674335A CN102674335A CN2012101643146A CN201210164314A CN102674335A CN 102674335 A CN102674335 A CN 102674335A CN 2012101643146 A CN2012101643146 A CN 2012101643146A CN 201210164314 A CN201210164314 A CN 201210164314A CN 102674335 A CN102674335 A CN 102674335A
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Abstract
The invention discloses a method for preparing graphene based on free radical reaction at low temperature, relateing to a preparation method of a graphene film. The invention aims to solve the problems that in the prior method for preparing graphene by the chemical vapor deposition (CVD) technology, the reaction temperature is high, the cost is high, the yield is low, the consumption time is long, and the required experimental condition is strict. The operation steps of the method are as follows: 1, selecting a proper carbon source; 2, treating and catalyzing a substrate surface; 3, preparing the graphene film; and 4, transferring the graphene to the needed substrate. When the method introduces the solid carbon source to the CVD technology to prepare the graphene film, the method takes the carbon source as the carbon source, and then prepares the single-layer uniform graphene film on the copper substrate. The method improves the method for preparing graphene by the CVD technology, and improves the yield and the quality of the prepared graphene film.
Description
Technical field
The present invention relates to a kind of preparation method of graphene film.
Background technology
Graphene (Graphene) is a kind of new carbon of finding in 2004, and its carbon atom is with sp
2Mode hydridization forms hexagon solid matter shape two dimensional crystal structure, does not become key P track on whole plane, to form big π key at carbon atom on the two dimensional surface.Particular structure makes Graphene have a series of special electricity, optics, mechanical property.Can reach 2 * 10 like its mobility of charge carrier speed
5Cm
2.V
-1.s
-1, fast 100 times than silicon, fast 20 times than gallium arsenide, and not with temperature variation; Electronic motion speed is up to 1 * 10 in Graphene
6M/s is far longer than the movement velocity of electronics in other conductor; Young's modulus is 200 times of structure iron up to 1060GPa.In addition, internal absorption factor is merely 2.3% to single-layer graphene in the visible region.These excellent performances of Graphene make it gather around at aspects such as nano electron device, matrix material, electrode materialss and have broad application prospects.
The advantage of Graphene: 1, the Graphene specific surface area is up to 2630m
2/ g, the atom of forming Graphene is easy to adatom and molecule all on its surface, makes it in atmosphere storage, is widely used in the high sensor; 2, conduct electricity very well, come from the carrier transport speed of Graphene itself; 3, intensity is high, and Graphene has the Young's modulus of 1060GPa, makes graphene film have excellent mechanical intensity; 4, the very little transmittance of graphene film thickness is high, and the Graphene of individual layer is merely 0.34nm, and transmittance is widely used it greater than 97% during 550nm aspect transparent electrode material; 5, stability is high, because the Graphene particular structural makes can in the environment of temperature less than 5K, keep electroconductibility again by Graphene ability stable existence in the 900K air.So graphene film has good prospects for application at aspects such as protein detection, biochemistry detection, electrode materials, gas sensing, matrix materials.And graphene film is mixed, can change many electrical properties such as its carrier concentration, electronic mobility and ability bandwidth bandwidth, be very helpful to widening its range of application.
The method for preparing at present graphene film mainly contains mechanically peel method, chemical stripping method, epitaxial growth method, chemical Vapor deposition process (CVD).Their each tool advantages within the specific limits, but also have shortcoming, can prepare the Graphene of micron size like the Graphene method of using the preparation of mechanically peel method; But its controllability is lower; And productive rate is very low, is difficult to prepare single-layer graphene, is difficult to realize extensive synthetic.And the employing epitaxial growth method; As passing through heating SiC (0001) single-crystal surface extending and growing graphene structure on the SiC surface; Though this Graphene that supports can directly be made electron device through photoetching process; But because reconstruct takes place easily on SiC plane of crystal surface in high-temperature heating process, cause surface tissue comparatively complicated, be difficult to obtain the Graphene of big area, uniform in thickness.And chemical Vapor deposition process (CVD) is though provide a valid approach to come approach controllably synthetic and the preparation graphene film; But its growth temperature is all more than 1000 ℃; This had both increased preparation cost and time, was that material is had higher requirement to apparatus for preparation also.Temperature of reaction is high, cost is high, productive rate is low so the graphene film technology of preparing of prior art for preparing exists, length consuming time, require the harsh problem of experiment condition.
Summary of the invention
For the graphene film technology of preparing that solves prior art for preparing exists that temperature of reaction is high, cost is high, productive rate is low, length consuming time, require the harsh problem of experiment condition, the present invention provides a kind of method for preparing Graphene based on free radical reaction low temperature.
Of the present inventionly prepare the method for Graphene, accomplish according to the following steps based on free radical reaction low temperature:
One, handle the catalytic substrate surface:
1., be the size that the plate shears of 25 ~ 200 μ m is cut into to be needed with thickness, and put it in the container that Glacial acetic acid min. 99.5 is housed; Be placed on target temperature then and be hot platform heating 5 ~ 30min down of 30 ~ 60 ℃;
2., the tinsel of step in 1. taken out from container, and Glacial acetic acid min. 99.5 is cleaned with deionized water;
3., the tinsel of step in 2. put into baking oven dry, for use;
Two, preparation graphene film:
1., the tinsel of being handled well in the step 1 and carbon source are put into the different heating section position of vacuum tube furnace respectively, the isolated temperature of silica wool is put in the centre;
2., vacuum tube furnace is pumped into low pressure with vacuum pump, be 0.001 ~ 0.02 standard atmospheric pressure, feed hydrogen and argon gas then the carbon source catalyst substrate is protected, the throughput ratio of hydrogen and argon gas is 1:1 ~ 10, and keeps the low-pressure state in the tube furnace;
3., open the heated zones that tinsel is in, be heated to 1035 ℃, under this temperature, keep 20 ~ 30min, tinsel is taken off fire handles;
4., stop the heating, tinsel is naturally cooled to 200 ~ 600 ℃, heat the heated zones that carbon source is positioned simultaneously, be heated to 90 ~ 110 ℃, carbon source steam contacts with tinsel with flow hydrogen gas and reacts, the reaction times is 5 ~ 30min;
5. stop heating, tube furnace is naturally cooled to room temperature;
Three, shift Graphene to required substrate:
1., the tinsel base that has graphene film of step 2 preparation is taken out from tube furnace, putting into the spin coating appearance drips the methyl-phenoxide solution that contains PMMA and carries out spin coating;
2., the tinsel of step in 1. put into oxygen plasma etching machine etching 30s ~ 5min;
3., the tinsel of step in 2. put into the iron trichloride etching liquid and carry out etching 12h ~ 24h;
4., the PMMA/ graphene film in the vessel is cleaned more than three times, with the required target substrate that is transferred to the graphene film in the etching liquid is picked up again, put into acetone then and soak 12h ~ 24h, to remove PMMA with deionized water;
5., take out the Graphene shifted, oven dry promptly obtains final finished.
The present invention introduces solid carbon source in the process of chemical Vapor deposition process (CVD) technology preparation graphene film, is carbon source with the carbon source, in the copper substrate, prepares the graphene film of individual layer homogeneous.This method improvement chemical Vapor deposition process (CVD) preparation Graphene technology, improved the productive rate and the quality of the graphene film of preparation.The present invention has following advantage:
One, method provided by the invention is compared with traditional chemical Vapor deposition process (CVD), has significantly reduced temperature of reaction, plant and instrument is required less, and speed of reaction significantly improves, and cost has reduced more than 50%;
Two, the graphene film major part of the present invention's preparation is uniform single-layer graphene, and the transmittance of the graphene film of the present invention's preparation is greater than 97%;
Three, the present invention can extensive integrated preparation graphene film, and the size of graphene film depends on the size of used tinsel fully;
Four, the present invention can carry out the doping of different substances to Graphene through adopting different substances as carbon source, reaches the purpose of the modification of Graphene, with the type of current carrier in the regulation and control graphene film;
Five, the individual layer of the graphene oxide of the present invention's preparation is greater than 85%.
Description of drawings
Fig. 1 is that the graphene film of embodiment 21 preparations shifts the camera photograph in the PET substrate;
Fig. 2 is that the graphene film of embodiment 21 preparations shifts the transmittance at PET substrate different wave length in visible region;
Fig. 3 is that the graphene film of embodiment 21 preparations shifts the optical microscope photograph in silica-primed;
Fig. 4 is that the graphene film of embodiment 21 preparations shifts the Raman spectrogram in silica-primed;
Fig. 5 is based on the schematic diagram that the technological low temperature of chemical Vapor deposition process (CVD) prepares the method for Graphene;
Fig. 6 is the electron microscope scanning figure of 6000 times of the graphene films of embodiment 21 preparation;
Fig. 7 is the high resolution X-ray photoelectron spectroscopic analysis figure of the nitrating graphene film of embodiment 21 preparations at 394 ~ 410 ev.
Embodiment
Embodiment one: this embodiment provides a kind of and has prepared the method for Graphene based on the technological low temperature of chemical Vapor deposition process (CVD), and it is accomplished according to the following steps:
1., select to be easy to the carbon source that free radical reaction takes place and be easy to form the Graphene Web materials one, select suitable carbon source:, the polynary carbon cpd of therefore selecting to contain halogen atom will become suitable carbon source, like chloro or bromobenzene, naphthalene, phenanthrene or anthracene etc.; 2., heterogeneous ring compound (nitrogenous, sulphur, phosphorus, the silicon etc.) compound of selecting to contain other elements is as carbon source; Come the graphene film of preparation is mixed; To reach the purpose of it being carried out modification, graphene film is mixed other element as adopting halogenated furans, pyridine or thiophene.
1., be that the plate shears of 25 ~ 200 μ m is cut into the size that needs two, handle the catalytic substrate surface:, and put it in the container that Glacial acetic acid min. 99.5 is housed with thickness; Be placed on target temperature then and be heating 5 ~ 30min under 30 ~ 60 ℃ hot platform; 2., the tinsel of step in 1. taken out from container, and Glacial acetic acid min. 99.5 is cleaned with deionized water; 3., the tinsel of step in 2. put into baking oven dry, for use.The tinsel of step in 1. can be elements such as nickel, copper, platinum, cobalt, gold, palladium.
Three, preparation graphene film: 1., the tinsel of being handled well in the step 2 and carbon source put into the different heating section position of vacuum tube furnace respectively; The isolated temperature of silica wool is put in the centre; Wherein the carbon source quality was decided according to the reaction times, was specially carbon source quality (mg): the reaction times (min)=5 ~ 20:1; 2., vacuum tube furnace is pumped into low pressure, be about 0.001 ~ 0.02 standard atmospheric pressure, feed hydrogen and argon gas then the carbon source catalyst substrate is protected, the throughput ratio of hydrogen and argon gas is 1:1 ~ 10, and keeps the low-pressure state in the tube furnace with vacuum pump; 3., open the heated zones that tinsel is in, be heated to 1035 ℃, under this temperature, keep 20min, tinsel is taken off fire handles; 4., stop the heating, tinsel is naturally cooled to 200 ~ 600 ℃, heat the heated zones that carbon source is positioned simultaneously, be heated to 90 ~ 110 ℃.Carbon source steam contacts with tinsel with flow hydrogen gas and reacts, and the reaction times is 5 ~ 30min; 5. stop heating, tube furnace is naturally cooled to room temperature.
Four, shift Graphene to required substrate: 1., the tinsel base that has graphene film of step 3 preparation is taken out, put into the spin coating appearance and drip the methyl-phenoxide solution that contains PMMA and carry out spin coating from tube furnace; 2., the tinsel of step in 1. put into oxygen plasma etching machine etching 30s ~ 5min; 3., the tinsel of step in 2. put into the iron trichloride etching liquid and carry out the about 12h of etching; 4., the PMMA/ graphene film in the vessel is cleaned more than three times, with the required target substrate that is transferred to the graphene film in the etching liquid is picked up again, put into acetone immersion 12h then to remove PMMA with deionized water; 5., take out the Graphene shifted, oven dry promptly obtains final finished.The mass ratio of PMMA and methyl-phenoxide is 1:12 ~ 20 in the spin coating liquid of step in 1., and more than dissolving 0.5h under 80 ℃ of water bath condition, spin coating revolution and time are 4000r/min, 5s, then 8000r/min 30s.Each constituent mass is than being iron trichloride in the 3. middle etching liquid of step: concentrated hydrochloric acid: deionized water=3.5:10:100.
Embodiment two: this embodiment with the difference of embodiment one is: step 2 1. sheet thicknesses is 25 ~ 100 μ m, and puts it in the container that Glacial acetic acid min. 99.5 is housed; Be placed on target temperature then and be heating 10 ~ 20min under 35 ~ 50 ℃ hot platform.Other is identical with embodiment one.
Embodiment three: this embodiment with one of embodiment one to two difference is: step 2 1. sheet thicknesses is 25 ~ 40 μ m, and puts it in the container that Glacial acetic acid min. 99.5 is housed; Be placed on target temperature then and be heating 12 ~ 18min under 40 ~ 45 ℃ hot platform.Other is identical with embodiment one or two.
Embodiment four: this embodiment with one of embodiment one to three difference is: step 2 1. sheet thicknesses is 25 μ m, and puts it in the container that Glacial acetic acid min. 99.5 is housed; Be placed on target temperature then and be heating 15min under 42 ℃ hot platform.Other is identical with embodiment one or three.
Embodiment five: this embodiment with one of embodiment one to four difference is: step 3 is carbon source quality (mg) 1.: the reaction times (min)=8 ~ 15:1.Other is identical with embodiment one or four.
Embodiment six: this embodiment with one of embodiment one to five difference is: step 3 is carbon source quality (mg) 1.: the reaction times (min)=10:1.Other is identical with embodiment one or five.
Embodiment seven: one of this embodiment and embodiment one to six difference is: the low pressure environment of step 3 described in 2. is 0.005 ~ 0.015 standard atmospheric pressure.Other and embodiment one or six phase with.
Embodiment eight: one of this embodiment and embodiment one to seven difference is: the low pressure environment of step 3 described in 2. is 0.01 standard atmospheric pressure.Other is identical with embodiment one or seven.
Embodiment nine: one of this embodiment and embodiment one to eight difference is: the feeding hydrogen of step 3 described in 2. and the throughput ratio of argon gas are 1:2 ~ 5.Other is identical with embodiment one or eight.
Embodiment ten: one of this embodiment and embodiment one to nine difference is: the feeding hydrogen of step 3 described in 2. and the throughput ratio of argon gas are 1:3.Other is identical with embodiment one or nine.
Embodiment 11: one of this embodiment and embodiment one to ten difference is: the temperature of tinsel is 300 ~ 500 ℃ during the preparation feedback of step 3 described in 4..Other is identical with embodiment one or ten.
Embodiment 12: one of this embodiment and embodiment one to 11 difference is: the temperature of tinsel is 400 ℃ during the preparation feedback of step 3 described in 4..Other is identical with embodiment one or 11.
Embodiment 13: one of this embodiment and embodiment one to 12 difference is: the heated zones that the heating carbon source of step 3 described in 4. is positioned is heated to 95 ~ 105 ℃.Other is identical with embodiment one or 12.
Embodiment 14: one of this embodiment and embodiment one to 13 difference is: the heated zones that the heating carbon source of step 3 described in 4. is positioned is heated to 100 ℃.Other is identical with embodiment one or 13.
Embodiment 15: this embodiment with one of embodiment one to 13 difference is: the carbon source steam of step 3 described in 4. contacts with tinsel with flow hydrogen gas and reacts, and the reaction times is 10 ~ 20min.Other is identical with embodiment one or 14.
Embodiment 16: this embodiment with one of embodiment one to 15 difference is: the carbon source steam of step 3 described in 4. contacts with tinsel with flow hydrogen gas and reacts, and the reaction times is 15min.Other is identical with embodiment one or 15.
Embodiment 17: one of this embodiment and embodiment one to 16 difference is: the mass ratio of PMMA and methyl-phenoxide is 1:14 ~ 18 in the spin coating liquid of step 4 in 1..Other and embodiment one or ten six phases with.
Embodiment 18: one of this embodiment and embodiment one to 17 difference is: the mass ratio of PMMA and methyl-phenoxide is 1:15 in the spin coating liquid of step 4 in 1..。Other is identical with embodiment one or 17.
Embodiment 19: one of this embodiment and embodiment one to 18 difference is: the tinsel of step 4 in 2. put into oxygen plasma etching machine etching 1 ~ 3min.Other is identical with embodiment one or 18.
Embodiment 20: one of this embodiment and embodiment one to 19 difference is: the tinsel of step 4 in 2. put into oxygen plasma etching machine etching 1.5min.Other is identical with embodiment one or 19.
Embodiment 21: as shown in Figure 5, this embodiment provides a kind of method for preparing Graphene based on chemical Vapor deposition process (CVD) technology
,Specifically accomplish according to the following steps:
One, select suitable carbon source: this embodiment adopts chloro-pyridine as carbon source.
1., be that the nickel tinsel of 25 μ m is put into the container that Glacial acetic acid min. 99.5 is housed two, handle the catalytic substrate surface: with thickness; Be placed on target temperature then and be heating 15min under 42 ℃ hot platform; 2., the tinsel in will be 1. takes out from container, and with deionized water Glacial acetic acid min. 99.5 is cleaned.3., the tinsel in will be is 2. put into baking oven dries, and is for use.
Three, preparation graphene film: 1., the tinsel of being handled well in the step 1 and carbon source put into the different heating section position of vacuum tube furnace respectively; The isolated temperature of silica wool is put in the centre; Wherein the carbon source quality was decided according to the reaction times, was specially carbon source quality (mg): the reaction times (min)=5:1 ~ 20:1; 2., vacuum tube furnace is pumped into low pressure, be about 0.001 ~ 0.02 standard atmospheric pressure, feed hydrogen and argon gas then the carbon source catalyst substrate is protected, the throughput ratio of hydrogen and argon gas is 1:1 ~ 1:10, and keeps the low-pressure state in the tube furnace with vacuum pump; 3., open the heated zones that tinsel is in, be heated to 1035 ℃, under this temperature, keep 20min, tinsel is taken off fire handles; 4., stop the heating, tinsel is naturally cooled to 200 ~ 600 ℃, heat the heated zones that carbon source is positioned simultaneously, be heated to 90 ~ 110 ℃.Carbon source steam contacts with tinsel with flow hydrogen gas and reacts, and the reaction times is 5min ~ 30min; 5., stop the heating, tube furnace is naturally cooled to room temperature.
Four, shift Graphene to required substrate: 1., the tinsel base that has graphene film of step 2 preparation is taken out, put into the spin coating appearance and drip the methyl-phenoxide solution that contains PMMA and carry out spin coating from tube furnace; 2., the tinsel of step in 1. put into oxygen plasma etching machine etching 1.5min; 3., the tinsel of step in 2. put into the iron trichloride etching liquid and carry out the about 12h of etching; 4., the PMMA/ graphene film in the vessel is cleaned more than three times, with the required target substrate that is transferred to the graphene film in the etching liquid is picked up again, put into acetone immersion 12h then to remove PMMA with deionized water; 5., take out the Graphene shifted, oven dry promptly obtains final finished.The mass ratio of PMMA and methyl-phenoxide is 1:15 in the spin coating liquid of step in 1., and more than dissolving 0.5h under 80 ℃ of water bath condition, spin coating revolution and time are 4000r/min 5s, then 8000r/min 30s; Each constituent mass ratio in the 3. middle etching liquid of step is iron trichloride: concentrated hydrochloric acid: deionized water=3.5:10:100.
The Graphene number of plies that this embodiment is prepared comparatively evenly has individual layer, bilayer or multilayer; But the multiwalled number of plies is all less than 10 layers; What promptly obtain is Graphene, and the ratio of conditional parameter and reactant makes the shared ratio of single-layer graphene greater than 85% in the strict regulation and control of this embodiment reaction process.
Shift the Graphene that comes out and have good transparency, see Fig. 1.Through the graphene film of this embodiment of uv-visible absorption spectroscopy test preparation, the observation transmittance is seen Fig. 2 greater than 97% when visible region.
Adopt the graphene film of surface sweeping electron microscope and this embodiment of observation by light microscope preparation, see Fig. 3 and Fig. 6, can see that this Graphene has good stratiform pattern and homogeneity.
Adopt Raman spectrum analysis method to characterize the graphene film of this embodiment preparation, prove that it is mainly single-layer graphene, see Fig. 4, I
G: I
2D<0.5, explain that it is a single-layer graphene.
Adopt the X-ray photoelectron spectroscopic analysis method to characterize the adulterated graphene film of nitrogen of this embodiment preparation, prove the doping that wherein contains the nitrogen element, see Fig. 7.
Claims (10)
1. one kind prepares the method for Graphene based on free radical reaction low temperature, it is characterized in that said method accomplishes according to the following steps:
One, handle the catalytic substrate surface:
1., be the size that the plate shears of 25 ~ 200 μ m is cut into to be needed with thickness, and put it in the container that Glacial acetic acid min. 99.5 is housed; Be placed on target temperature then and be hot platform heating 5 ~ 30min down of 30 ~ 60 ℃;
2., the tinsel of step in 1. taken out from container, and Glacial acetic acid min. 99.5 is cleaned with deionized water;
3., the tinsel of step in 2. put into baking oven dry, for use;
Two, preparation graphene film:
1., the tinsel of being handled well in the step 1 and carbon source are put into the different heating section position of vacuum tube furnace respectively, the isolated temperature of silica wool is put in the centre;
2., vacuum tube furnace is pumped into low pressure with vacuum pump, be 0.001 ~ 0.02 standard atmospheric pressure, feed hydrogen and argon gas then the carbon source catalyst substrate is protected, the throughput ratio of hydrogen and argon gas is 1:1 ~ 10, and keeps the low-pressure state in the tube furnace;
3., open the heated zones that tinsel is in, be heated to 1035 ℃, under this temperature, keep 20 ~ 30min, tinsel is taken off fire handles;
4., stop the heating, tinsel is naturally cooled to 200 ~ 600 ℃, heat the heated zones that carbon source is positioned simultaneously, be heated to 90 ~ 110 ℃, carbon source steam contacts with tinsel with flow hydrogen gas and reacts, the reaction times is 5 ~ 30min;
5. stop heating, tube furnace is naturally cooled to room temperature;
Three, shift Graphene to required substrate:
1., the tinsel base that has graphene film of step 2 preparation is taken out from tube furnace, putting into the spin coating appearance drips the methyl-phenoxide solution that contains PMMA and carries out spin coating;
2., the tinsel of step in 1. put into oxygen plasma etching machine etching 30s ~ 5min;
3., the tinsel of step in 2. put into the iron trichloride etching liquid and carry out etching 12 ~ 24h;
4., the PMMA/ graphene film in the vessel is cleaned more than three times, with the required target substrate that is transferred to the graphene film in the etching liquid is picked up again, put into acetone then and soak 12h ~ 24h, to remove PMMA with deionized water;
5., take out the Graphene shifted, oven dry promptly obtains final finished.
2. according to claim 1ly prepare the method for Graphene, it is characterized in that said carbon source is the polynary carbon cpd that contains halogen atom based on free radical reaction low temperature.
3. according to claim 2ly prepare the method for Graphene, it is characterized in that the said polynary carbon cpd that contains halogen atom is chloro or bromobenzene, naphthalene, phenanthrene or anthracene based on free radical reaction low temperature.
4. according to claim 1ly prepare the method for Graphene, it is characterized in that said carbon source is the heterogeneous ring compound that contains other elements based on free radical reaction low temperature.
5. according to claim 4ly prepare the method for Graphene, it is characterized in that said heterogeneous ring compound is halogenated furans, pyridine or thiophene based on free radical reaction low temperature.
6. according to claim 1ly prepare the method for Graphene, it is characterized in that the tinsel during said step 1 1. is nickel, copper, platinum, cobalt, gold, palladium based on free radical reaction low temperature.
7. according to claim 1ly prepare the method for Graphene, it is characterized in that the carbon source quality during said step 2 was 1. decided according to the reaction times, be specially carbon source quality (mg): the reaction times (min)=5 ~ 20:1 based on free radical reaction low temperature.
8. according to claim 1ly prepare the method for Graphene, it is characterized in that the mass ratio of PMMA and methyl-phenoxide is 1:12 ~ 20 in the spin coating liquid during said step 3 1., more than dissolving 0.5h under 80 ℃ of water bath condition based on free radical reaction low temperature.
9. according to claim 1ly prepare the method for Graphene, it is characterized in that spin coating revolution and time are 4000r/min, 5s during said step 3 1., then 8000r/min 30s based on free radical reaction low temperature.
10. according to claim 1ly prepare the method for Graphene based on free radical reaction low temperature, it is characterized in that said step 3 3., each constituent mass is than being iron trichloride in the etching liquid: concentrated hydrochloric acid: deionized water=3.5:10:100.
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