CN101009222A - A method for making the carbon nano tube electronic part - Google Patents
A method for making the carbon nano tube electronic part Download PDFInfo
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- CN101009222A CN101009222A CN 200710063106 CN200710063106A CN101009222A CN 101009222 A CN101009222 A CN 101009222A CN 200710063106 CN200710063106 CN 200710063106 CN 200710063106 A CN200710063106 A CN 200710063106A CN 101009222 A CN101009222 A CN 101009222A
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Abstract
The invention discloses a method of producing carbon nanometer tube electronic elements; the method includes steps as following: 1) carbon nanometer tubes are distributed on the surface of base of the insulated dielectric layer; 2) metallic film is plated on the base of the insulated dielectric layer; 3) patterned self-packaged monolayer film is formed on the metallic film; 4) corrosion; 5) post treatment. Comparing with current method in literature, the invention possesses many unique advantages: the method is easy and without complex and expensive instrument; it belongs to parallel method and can proceed industry automatization and large scale integration; it can breach limit of photoetching technique and achieve the electrode space between of several dozens of nanometer; the operation condition is mild, it is at room temperature, so that chemical vapour deposition can not be used in low melting point metal can be avoided; the craft period is short, all the cause just needs about 5 hours; the efficient is high, cost is low, range of application is wide, it possesses capacious foreground of business.
Description
Technical field
The present invention relates to a kind of method for preparing carbon nano-tube electron device, particularly relate to and a kind ofly prepare carbon nanotube field-effect transistor and be the method that connects the electrode structure of lead with the carbon nano-tube.
Background technology
Nanotube has nano level diameter, is a kind of desirable one-dimensional material.Carbon nano-tube has the performance of various excellences, especially its electrical properties (Acc.Chem.Res., 2002,35,1035-1044).Carbon nano-tube shows as two types of metallicity and semiconductives because of its orientation and diameter different; Can use metallic carbon nano-tube to make lead-in wire, use the carbon nano-tube of semiconductive to make full carbon nano tube device as channel material.Carbon nano-tube can bear 10
9A/cm
2Current density, than the taller several magnitude of metal; Pretending between the carbon atom firmly makes the carbon nano tube surface defective seldom, and surperficial dangling bonds are seldom, this be other one-dimensional material can not compare, and in organic molecular device, organic molecule does not solve with good the contact all the time of metal.Therefore people seek to use carbon nano-tube as channel material, fabricating yard effect transistor and the method that it is integrated.
1998, first field-effect transistor based on carbon nano-tube was succeeded in developing (J.Tans, A.R.M.Verschueren, and C.Dekker, Nature (London) 393,49,1998.Martel, T.Schmidt, H.R.Shea, T.Hertel, and P.Avouris, Appl.Phys.Lett.73,2447,1998.).From then on, the research of this respect becomes global research focus.The problem that the field-effect transistor of carbon nano-tube faces as: contact resistance is too big, can't accurately locate, grid control ability is poor, only finds that problems such as P type field effect transistor have all obtained better solution, and has used carbon nanotube field-effect transistor to prepare simple logical circuit.
In the evolution of carbon nano-tube electron device, manufacturing technology will play final decisive action.The preparation method of the carbon nanotube field-effect transistor of bibliographical information mainly is divided into two classes: progressively type method and parallel type method.Progressively the type method has electron beam lithography, focused ion beam deposition and alternating current electrophoresis method etc., can position and make electrode to single-root carbon nano-tube, and shortcoming is that speed is too slow, needs special instrument, the expense costliness; The parallel type method has method such as direct growth on photoetching, mask evaporation, the electrode, and these methods are quick, once can make large-tonnage product, yet its expense is still higher.Following application develops to extensive integrated direction, press for a kind of simple, fast, high yield, high-performance, manufacture method cheaply.
Summary of the invention
The purpose of this invention is to provide a kind of method for preparing carbon nano-tube electron device.
The method for preparing carbon nano-tube electron device provided by the present invention comprises the steps:
1) make carbon nano-tube be distributed in insulation dielectric layer substrate surface;
2) in the substrate of insulation dielectric layer, plate metallic film;
3) self-assembled monolayer of formation patterning on metallic film;
4) etching
At different metallic films, select the chemical reagent that can play corrosion reaction for use with metallic film, etch away the metallic film part that does not have the self-assembled monolayer protection, expose the substrate of insulation dielectric layer;
5) reprocessing
Remove the self-assembled monolayer above the metallic film, obtain the carbon nano-tube electron device of metallic film as electrode material.
Wherein, the step 1) carbon nano-tube is distributed in the insulation dielectric layer substrate surface, and location mode can be selected direct surface growth or spin coating, dip-coating mode; The insulation dielectric layer is selected silicon dioxide, zirconium dioxide, hafnium oxide or strontium titanates.Step 2) method that plates metallic film is molecular beam epitaxy, hot evaporation, electron beam evaporation plating, magnetron sputtering, chemical plating or electrochemistry plating; The material of metallic film is selected from one or more in gold, silver, copper, platinum, ruthenium, nickel, zinc, palladium, aluminium, the titanium.The method of the self-assembled monolayer of step 3) patterning comprises that micro-contact-printing, nanometer dip in a lithographic method, scan-probe etching method, optical exposure method, surface scratch method; The material of self-assembled monolayer is selected from one or more in sulfhydryl compounds such as stearylmercaptan, sulfydryl hexadecylic acid and sulfydryl toluene and the octadecyl phosphoric acid.
Uv irradiation method, heating or plasma etching method are adopted in the step 4) reprocessing.
Another kind provided by the present invention prepares the method for carbon nano-tube field electronic device, comprises the steps:
1) make carbon nano-tube be distributed in insulation dielectric layer substrate surface;
2) depositing electrically conductive film
In the substrate of insulation dielectric layer, deposit layer of conductive film;
3) depositing metal films
Deposition layer of metal film on conductive film;
4) self-assembled monolayer of formation patterning on metallic film;
5) first etching
At different metallic films, select the chemical reagent that can play corrosion reaction for use with metallic film, etch away the metallic film part that does not have the self-assembled monolayer protection, expose lower conductive film;
6) etching again
Adopt corresponding chemical reagent that the lower conductive film that comes out is carried out etching again, rationally control the time of corrosion reaction, expose the substrate of insulation dielectric layer;
7) reprocessing
Remove metallic film and self-assembled monolayer above the conductive film, obtain having only the carbon nano-tube electron device of conductive film as electrode material.
Wherein, the step 1) carbon nano-tube is distributed in the insulation dielectric layer substrate surface, and location mode can be selected direct surface growth or spin coating, dip-coating mode; The insulation dielectric layer is selected silicon dioxide, zirconium dioxide, hafnium oxide or strontium titanates.Step 2) method of depositing electrically conductive film is molecular beam epitaxy, hot evaporation, electron beam evaporation plating, magnetron sputtering, chemical plating or electrochemistry plating, and the material of conductive film commonly used is selected from conducting polymer such as metal such as titanium, aluminium and polythiophene and carbon black, tin oxide, zinc oxide aluminum, ITO conductive film etc.The method that step 3) plates metallic film is molecular beam epitaxy, hot evaporation, electron beam evaporation plating, magnetron sputtering, chemical plating or electrochemistry plating; The material of metallic film is selected from gold, silver, copper, platinum, ruthenium, nickel, zinc, palladium, aluminium, titanium etc.The method of the self-assembled monolayer of step 4) patterning comprises that micro-contact-printing, nanometer dip in a lithographic method, scan-probe etching method, optical exposure method, surface scratch method; The material of self-assembled monolayer is selected from one or more in sulfhydryl compounds such as stearylmercaptan, sulfydryl hexadecylic acid and sulfydryl toluene and the octadecyl phosphoric acid.
It is mask that the present invention uses self-assembled monolayer, and prepares carbon nano-tube electron device in conjunction with wet chemical etch.Compare with existent method in the document, the inventive method has the advantage of a lot of uniquenesses: method is simple, does not need complicated and expensive instrument and equipment; The method that belongs to the parallel processing class can be carried out industrial automation and integrated on a large scale; Can break through the limit of photoetching technique, reach the electrode spacing of tens nanometer scale; The operating condition gentleness is reacted in room temperature, has avoided chemical vapour deposition (CVD) can not be applicable to the characteristics of low-melting-point metal; Process cycle is very short, and all processes only needs about five hours; The productive rate height, with low cost, have wide range of applications, possess the bright prospects of commercialization utilization.The present invention can produce a series of electrode structures that are applicable to research carbon nano-tube electricity transport property, is applicable to the carbon nanotube field-effect transistor of various parallel, intersections of preparation and circulus; Simultaneously, also can be used to prepare with the carbon nano-tube is the various electrode structures that connect lead.
Description of drawings
Fig. 1 is the direct method process chart;
Fig. 2 is the indirect method process chart;
Fig. 3-8 is the carbon nano tube device structure of different electrode spacings;
Fig. 9-12 is for comprising the carbon nano tube device structure of heterojunction;
Figure 13-16 is a single-root carbon nano-tube ring-type device architecture;
Figure 17-22 is many carbon nano-tube interdigitated electrode design;
Figure 23-26 is many carbon nano-tube parallel array structures;
Figure 27-46 is that the carbon nanotube electrode structure and the electric property of different electrode materials characterizes and analytic curve;
Embodiment
The method that the present invention prepares carbon nano-tube electron device has two kinds:
First method---direct method, process chart as shown in Figure 1, operating procedure is as follows:
1) make carbon nano-tube 2 be distributed in insulation dielectric layer substrate 1 surface
The substrate of customary insulation dielectric layer can be selected silicon dioxide, zirconium dioxide, hafnium oxide or strontium titanates etc., and this can adopt following dual mode:
A) directly at insulation dielectric layer substrate 1 superficial growth overlength carbon nano pipe 2
At insulation dielectric layer substrate surface growth overlength carbon nano pipe, length can be from several microns to Centimeter Level; Growth temperature is 800～1000 degrees centigrade; Growth time was greater than 10 minutes; Carbon source can be used ethanol, methane etc.; Use hydrogen to be reducing agent; High-purity argon gas is carrier gas.
B) at insulation dielectric layer substrate 1 surperficial dispersing Nano carbon tubes 2;
After the carbon nanotube separation purification processes, adopt dichloro-benzenes or dimethyl formamide equal solvent to carry out solution and disperse, be applied to insulation dielectric layer substrate surface with whirler then, make it to be uniformly dispersed.
2) plate metallic film 3
Can adopt the whole bag of tricks to plate metallic film, for example molecular beam epitaxy, hot evaporation, electron beam evaporation plating, magnetron sputtering and chemical plating and electrochemistry plating at the insulation dielectric layer substrate surface that is distributed with carbon nano-tube; The thickness of metallic film can change according to the instructions for use of institute's machined electrode, to tens nanometers, also can arrive micron level from several nanometers; The metal system that direct method can adopt mainly comprises: gold, silver, copper, platinum, ruthenium, nickel, zinc, palladium, aluminium, titanium etc. and laminated film thereof.
3) self-assembled monolayer 4 of formation patterning on metallic film 3
Adopt various feasible ways to form the self-assembled monolayer of patterning on the metallic film surface, common method has micro-contact-printing (Kumar, A.; Whitesides, G.M.Science 1994,263, and 60-62.), nanometer is dipped in an etching method (Piner, R.D.; Jin, Z.; Feng, X.; Hong, S.; Mirkin, C.A.Science 1999,283, and 661.), scan-probe etching method (Ross, C.B.; Sun, L.; Crooks, R.M.Langmuir 1993,9,632-636. Schoer, J.K.; Ross, C.B.; Crooks, R.M.; Corbitt, T.S.; Hampden-Smith, M.J.Langmuir 1994,10,615-618. Muller, W.T.; Klein, D.L.; Lee, T.; Clarke, J.; Mceven, P.L.; Schultz, P.G.Science, 1995,268,272-273.), optical exposure method (Wollman, E.W.; Kang, D.; Frisbie, C.D.; Lorkovic, I.M.; Wrighton, M.S.J.Am.Chem.Soc.1994,116,4395-4404.Huang, J.Y.; Dahlgren, D.A.; Hemminger, J.C.Langmuir 1994,10,626-628.Tarlov, M.J.; Burgess, D.R.F.; Gillen, G.J.Am.Chem.Soc.1993,115,5305-5306.), surface scratch method (Abbott, N.L.; Kumar, A.; Whitesides, G.M.Chem.Mater.1994,6,596-602.).
The patterning of self-assembled monolayer can come layout according to the needs that reality is used; There is the metal of self-assembled monolayer in subsequent step, will be protected, can be used as electrode and use; Can obtain different electrode spacings by the spacing that changes the self-assembled monolayer film figure, and then obtain the carbon nano-tube electron device of different channel lengths; The kind of self-assembled monolayer can be selected different chemical materials according to the requirement of used metal species and subsequent step, for example one or more in sulfhydryl compound such as stearylmercaptan, sulfydryl hexadecylic acid and sulfydryl toluene and the octadecyl phosphoric acid.
4) etching
At different metallic film 3, select the chemical reagent that can play corrosion reaction for use with metallic film, etch away metallic film 3 parts that do not have self-assembled monolayer 4 protections.In the etching process, rationally control the time of corrosion reaction, expose insulation dielectric layer substrate 1, at this moment, come out in the carbon nano-tube 2 of insulation dielectric layer 1 surface distributed also part, and, cover the layer of metal film above the unexposed carbon nano-tube part, become the electrode of carbon nano-tube;
5) reprocessing
Remove the self-assembled monolayer 4 above the metallic film 3, obtain having only the carbon nanotube field-effect transistor of conductive film 4 as electrode material; Used method is UV-irradiation, the plasma etching method of suitable dose or the heat decomposition temperature that is heated to used self-assembled monolayer.
For those can with the electrode material of mask molecule chemically reactive, can use direct method, mask when directly on electrode material, forming self-assembled monolayer as chemical etching, thereby obtain the carbon nano tube device structure, for example, for gold, can form self-assembled film with stearylmercaptan, can be the carbon nano tube device structure of electrode material with the gold with the direct method preparation.
Second method---indirect method, process chart as shown in Figure 2, operating procedure is as follows:
1) make carbon nano-tube 2 be distributed in insulation dielectric layer substrate 1 surface
The substrate of customary insulation dielectric layer can be selected silicon dioxide, zirconium dioxide, hafnium oxide or strontium titanates etc., and this can adopt following dual mode:
A) directly at insulation dielectric layer substrate 1 superficial growth overlength carbon nano pipe 2
At insulation dielectric layer substrate surface growth overlength carbon nano pipe, length can be from several microns to Centimeter Level; Growth temperature is 800～1000 degrees centigrade; Growth time was greater than 10 minutes; Carbon source can be used ethanol, methane etc.; Use hydrogen to be reducing agent; High-purity argon gas is carrier gas.
B) at insulation dielectric layer substrate 1 surperficial dispersing Nano carbon tubes 2;
After the carbon nanotube separation purification processes, adopt dichloro-benzenes or dimethyl formamide equal solvent to carry out solution and disperse, be applied to insulation dielectric layer substrate surface with whirler then, make it to be uniformly dispersed.
2) the depositing electrically conductive film 31
Can adopt the whole bag of tricks being distributed with the insulation dielectric layer substrate surface depositing electrically conductive film 31 of carbon nano-tube, for example molecular beam epitaxy, hot evaporation, electron beam evaporation plating, magnetron sputtering and chemical plating, electrochemistry plating and chemical vapour deposition (CVD); The thickness of conductive film 31 can change according to the instructions for use of institute's machined electrode, to tens nanometers, also can arrive micron level from several nanometers; The conductive film system that indirect method can adopt is applicable to all metals and other non-metallic conducting material, and commonly used have conducting polymer, carbon black, tin oxide, zinc oxide aluminum, ITO conductive films etc. such as metal such as titanium, aluminium and polythiophene.
3) depositing metal films 3
Can adopt the whole bag of tricks on conductive film 31, to plate metallic film 3, for example molecular beam epitaxy, hot evaporation, electron beam evaporation plating, magnetron sputtering and chemical plating and electrochemistry plating; The thickness of metallic film 3 can for several nanometers to tens nanometers, also can arrive micron level; The metal system that can adopt mainly comprises: gold, silver, copper, platinum, ruthenium, nickel, zinc, palladium, aluminium, titanium etc.
4) self-assembled monolayer 4 of formation patterning on metallic film
Adopt various feasible ways to form the self-assembled monolayer 4 of patterning on metallic film 3 surfaces, common method has micro-contact-printing, and nanometer is dipped in an etching method, scan-probe etching method, optical exposure method, surface scratch method.
The patterning of self-assembled monolayer can come layout according to the needs that reality is used; There is the metal of self-assembled monolayer in subsequent step, will be protected; Can obtain different electrode spacings by the spacing that changes the self-assembled monolayer film figure, and then obtain the carbon nano-tube electron device of different channel lengths; The kind of self-assembled monolayer can be selected different chemical materials according to the requirement of used metal species and subsequent step, for example one or more in sulfhydryl compound such as stearylmercaptan, sulfydryl hexadecylic acid and sulfydryl toluene and the octadecyl phosphoric acid.
5) first etching
At different metallic film 3, select the chemical reagent that can play corrosion reaction for use with metallic film, etch away metallic film 3 parts that do not have self-assembled monolayer 4 protections; The time of control corrosion reaction rationally, expose lower conductive film 31.
6) adopt chemical reagent to carry out etching again
Adopt corresponding chemical reagent that the lower conductive film 31 that comes out is carried out etching again, the time of control corrosion reaction rationally, expose insulation dielectric layer substrate 1, also partly come out in the carbon nano-tube 2 that insulation dielectric layer substrate surface distributes this moment, and, cover layer of conductive film above the unexposed part carbon nano-tube, become the electrode of carbon nano-tube;
7) reprocessing
Remove metallic film 3 and self-assembled monolayer 4 above the conductive film, obtain having only the carbon nano-tube electron device of conductive film 31 as electrode material; Removing the used method of self-assembled monolayer is the UV-irradiation of suitable dose or heat decomposition temperature or the plasma etching that is heated to used self-assembled monolayer; Remove the method for metallic film and will select corresponding chemical reagent according to its kind.
For those can not with the electrode material of mask molecule chemically reactive, then can not adopt direct method, need to adopt indirect method to prepare carbon nano tube device, promptly on this electrode material, plate earlier the layer of metal film, mask when on this metallic film, forming self-assembled monolayer again as chemical etching, thus the carbon nano tube device structure obtained.For example, for titanium, can not form self-assembled film with stearylmercaptan, can not be the carbon nano tube device structure of electrode material with the titanium with the direct method preparation, will prepare with indirect method.
Adopt above method, according to the spread pattern of different carbon nano-tube, and the different distance between the self-assembled monolayer sets, and can obtain the carbon nano tube device of different structure.For example, in preparation process, the carbon nano-tube between electrode can be designed to different structures, as various circuluses, to adapt to the actual instructions for use of carbon nano-tube electron device; Also can be between electrode many carbon nano-tube being arranged is various parallel, chi structures, to realize the array structure of carbon nano-tube electron device; Perhaps, adjust the spacing between the electrode, preparation has the carbon nano tube device structure of various spacings; Perhaps, heterojunction is set between electrode, comprises the carbon nano tube device structure of heterojunction between the preparation electrode.
Fig. 3-8 is the carbon nano tube device structure of different electrode spacings, is respectively that electrode spacing is the electromicroscopic photograph of the carbon nano tube device of 40,30,20,10,5,1 μ m; Fig. 9-12 is respectively the electromicroscopic photograph that has a block trim, two block trims, a banded trim and contain the carbon nano tube device of a banded trim between two carbon nano-tube for comprising the carbon nano tube device structure of heterojunction; Figure 13-16 is a single-root carbon nano-tube ring-type device architecture, is respectively single-root carbon nano-tube and forms a loop configuration, single-root carbon nano-tube and form a loop configuration, single-root carbon nano-tube and form the electromicroscopic photograph that two loop configuration and two carbon nano-tube respectively form the carbon nano tube device of a loop configuration; Figure 17-22 is many carbon nano-tube interdigitated electrode design, Figure 17 is the electromicroscopic photograph that three carbon nano-tube form chi structure, Figure 18 is the enlarged drawing of Figure 17, Figure 19 is the chi structure of two carbon nano-tube, Figure 20 is the electromicroscopic photograph of the chi structure of three carbon nano-tube, and Figure 21 and Figure 22 are respectively the chi structure of four carbon nano-tube; Figure 23-26 is many carbon nano-tube parallel array structures, is respectively the electromicroscopic photograph of two carbon nano-tube parallel arrays of 40 μ m-, three carbon nano-tube parallel arrays, four carbon nano-tube parallel arrays and five carbon nano-tube parallel arrays.
Here, can also adopt the multistep combined techniques to prepare carbon nano-tube electron device: employing two kinds of methods as mentioned above obtains can repeat wherein class methods after the electrode structure on this basis, obtains more complex multilayered structures.
The carbon nano-tube electron device that the inventive method is prepared, according to selected carbon nano-tube performance difference, also has different performances: when used carbon nano-tube is semiconductor type carbon nano-tube, gained is a carbon nanotube field-effect transistor, characteristic with field effect transistor shows extremely low cut-off current and high on-off ratio; Adopting golden titanium electrode system gained field effect transistor mainly is p type carbon nanotube field-effect transistor and ambipolar carbon nanotube field-effect transistor, and can obtain n type carbon nanotube field-effect transistor and ambipolar carbon nanotube field-effect transistor when adopting aluminium for electrode system.Also can select other different electrode material as required for use, obtain dissimilar carbon nanotube field-effect transistors.When used carbon nano-tube was the metal mold carbon nano-tube, gained can be applicable to make on a large scale the carbon nano-tube integrated circuit for being the electrode structure that connects lead with the carbon nano-tube.
Below with specific embodiment preparation process of the present invention is described.
Embodiment 1: adopting Au/Cr is carbon nano-tube two terminal device and the field-effect transistor that electrode material is made
The detailed process of preparation is:
1) directly at silicon dioxide substrate surface growth overlength carbon nano pipe;
At silicon dioxide substrate surface growth overlength carbon nano pipe, length is from several microns to about one centimetre; Growth temperature is 800～1000 degrees centigrade; Growth time is more than 10 minutes; Carbon source is used ethanol; Use hydrogen to be reducing agent; High-purity argon gas is carrier gas.
2) plate metallic film
Can adopt hot evaporation to belong to film: to plate the about 10nm of one deck chromium thickness earlier, plate the about 80nm of one deck gold thickness again in the silicon dioxide substrate surface plated with gold that is distributed with carbon nano-tube.The thickness of metallic film can change according to the instructions for use of institute's machined electrode, from several nanometers to several micron.
3) self-assembled monolayer of formation patterning on metallic film
Adopt micro-contact-printing to form the self-assembled monolayer of patterning on the metallic film surface.Used masterplate material is PDMS; There is the metal of self-assembled monolayer in subsequent step, will be protected, can be used as electrode and use; Can obtain different electrode spacings by the spacing that changes the self-assembled monolayer film figure, and then obtain the carbon nanotube field-effect pipe of different channel lengths; The kind of self-assembled monolayer is a stearylmercaptan.
4) etching
Select the chemical reagent that can play corrosion reaction---the mixed solution of 1M potassium hydroxide and 0.1M potassium thiosulfate for use, etch away the metallic film part that does not have the self-assembled monolayer protection with golden chromium thin film.In the etching process, the time of control corrosion reaction rationally is half an hour to one hour, expose the silicon dioxide substrate, at this moment, the carbon nano-tube that distributes at silica surface also partly comes out, and, cover the layer of metal film above the unexposed carbon nano-tube part, become the electrode of carbon nano-tube;
5) reprocessing
Remove the self-assembled monolayer above the metallic film, obtain carbon nano-tube electron device; Used method kept about 10 minutes for being heated to 200 degrees centigrade.
Adopt Au/Cr be the electrode structure made of electrode material shown in Figure 27,29, Figure 28 be the electrology characteristic curve of electrode structure shown in Figure 27, this carbon nano-tube shows metallicity, plays the connection lead; Figure 30 is the electrology characteristic curve of electrode structure shown in Figure 29, and this carbon nano-tube shows semiconductive, is a field effect transistor.
Embodiment 2: adopting Au/Ti is carbon nano-tube two terminal device and the field-effect transistor that electrode material is made
The detailed process of preparation is:
1) directly at silicon dioxide substrate surface growth overlength carbon nano pipe;
At silicon dioxide substrate surface growth overlength carbon nano pipe, length is from several microns to about one centimetre; Growth temperature is 800～1000 degrees centigrade; Growth time is more than 10 minutes; Carbon source is used ethanol; Use hydrogen to be reducing agent; High-purity argon gas is carrier gas.
2) plate metallic film
Can adopt hot evaporation to belong to film: to plate the about 10nm of one deck titanium thickness earlier, plate the about 40～80nm of one deck gold thickness again in the silicon dioxide substrate surface plated with gold that is distributed with carbon nano-tube.The thickness of metallic film can change according to the instructions for use of institute's machined electrode, from several nanometers to several micron.
3) self-assembled monolayer of formation patterning on metallic film
Adopt nanometer to dip in an etching method forms patterning on the metallic film surface self-assembled monolayer.Used masterplate material is PDMS; There is the metal of self-assembled monolayer in subsequent step, will be protected, can be used as electrode and use; Can obtain different electrode spacings by the spacing that changes the self-assembled monolayer film figure, and then obtain the carbon nanotube field-effect pipe of different channel lengths; The kind of self-assembled monolayer is a stearylmercaptan.
4) etching
Select chemical reagent---the mixed solution of 1M potassium hydroxide and 0.1M potassium thiosulfate that can play corrosion reaction for use with golden titanium film; in the etching process; the time of control corrosion reaction rationally is half an hour to one hour; at first etch away the gold thin film part that does not have self-assembled monolayer protection, fall the titanium film portion with 1% hf etching then.Expose the silicon dioxide substrate at last, at this moment, the carbon nano-tube that distributes at silica surface also partly comes out, and, cover the layer of metal film above the unexposed carbon nano-tube part, become the electrode of carbon nano-tube;
5) reprocessing
Remove the self-assembled monolayer above the metallic film, obtain carbon nano-tube electron device; Used method kept about 10 minutes for being heated to 200 degrees centigrade.
Adopting Au/Ti is that the electrode structure made of electrode material is shown in Figure 31,33, Figure 32 is the electrology characteristic curve of electrode structure shown in Figure 31, this carbon nano-tube shows metallicity, play a part to connect lead, measure its IV specificity analysis such as Figure 41 and show that this golden titanium diagram of system reveals high electric conductivity; Figure 34 is the electrology characteristic curve of electrode structure shown in Figure 33, and this carbon nano-tube shows semiconductive, is a field effect transistor, and logarithmic curve analysis such as Figure 42 show that this golden titanium diagram of system reveals high on-off ratio 10
6-10
7
Embodiment 3: adopting Pd/Ti is carbon nano-tube two terminal device and the field-effect transistor that electrode material is made
The detailed process of preparation is:
1) directly at silicon dioxide substrate surface growth overlength carbon nano pipe;
At silicon dioxide substrate surface growth overlength carbon nano pipe, length is from several microns to about one centimetre; Growth temperature is 800～1000 degrees centigrade; Growth time is more than 10 minutes; Carbon source is used ethanol; Use hydrogen to be reducing agent; High-purity argon gas is carrier gas.
2) plate metallic film
Can adopt magnetron sputtering to belong to film: to plate the about 10nm of one deck titanium thickness earlier, plate the about 90nm of one deck palladium thickness again in the silicon dioxide substrate surface plated with gold that is distributed with carbon nano-tube.The thickness of metallic film can change according to the instructions for use of institute's machined electrode, from several nanometers to several micron.
3) self-assembled monolayer of formation patterning on metallic film
Adopt the scan-probe etching method to form the self-assembled monolayer of patterning on the metallic film surface.Used masterplate material is PDMS; There is the metal of self-assembled monolayer in subsequent step, will be protected, can be used as electrode and use; Can obtain different electrode spacings by the spacing that changes the self-assembled monolayer film figure, and then obtain the carbon nanotube field-effect pipe of different channel lengths; The kind of self-assembled monolayer is a stearylmercaptan.
4) etching
Select the chemical reagent that can play corrosion reaction---the mixed solution of 1M ferric trichloride and 0.1M hydrochloric acid for use with palladium membranes, in the etching process, the time of control corrosion reaction rationally is half an hour to one hour, at first etch away the palladium membranes part that does not have the self-assembled monolayer protection, fall the titanium film portion with 1% hf etching then, expose the silicon dioxide substrate at last, at this moment, the carbon nano-tube that distributes at silica surface also partly comes out, and, cover one deck palladium/platinum/titanium metal thin film above the unexposed carbon nano-tube part, become the electrode of carbon nano-tube;
5) reprocessing
Remove the self-assembled monolayer above the metallic film, obtain carbon nano-tube electron device; Used method kept about 10 minutes for being heated to 200 degrees centigrade.
Adopt palladium/titanium be the electrode structure made of electrode material as shown in figure 35, Figure 36 be the electrology characteristic curve of electrode structure shown in Figure 35, this carbon nano-tube shows metallicity, plays the connection lead.
Embodiment 4: adopting A1 is carbon nano-tube two terminal device and the field-effect transistor that electrode material is made
The detailed process of preparation is:
1) directly at silicon dioxide substrate surface growth overlength carbon nano pipe;
At silicon dioxide substrate surface growth overlength carbon nano pipe, length is from several microns to about one centimetre; Growth temperature is 800～1000 degrees centigrade; Growth time is more than 10 minutes; Carbon source is used ethanol; Use hydrogen to be reducing agent; High-purity argon gas is carrier gas.
2) plate metallic film
Can adopt electron beam evaporation plating to belong to film: directly to plate the about 80nm of layer of aluminum thickness in the silicon dioxide substrate surface plated with gold that is distributed with carbon nano-tube.The thickness of metallic film can change according to the instructions for use of institute's machined electrode, from several nanometers to several micron;
3) self-assembled monolayer of formation patterning on metallic film
Adopt the optical exposure method to form the self-assembled monolayer of patterning on the metallic film surface.Used masterplate material is PDMS; There is the metal of self-assembled monolayer in subsequent step, will be protected, can be used as electrode and use; Can obtain different electrode spacings by the spacing that changes the self-assembled monolayer film figure, and then obtain the carbon nanotube field-effect pipe of different channel lengths; The kind of self-assembled monolayer is one or more in the octadecyl phosphoric acid.
4) etching
Select chemical reagent---the 1M potassium hydroxide solution that can play corrosion reaction for use, etch away the metallic film part that does not have the self-assembled monolayer protection with the aluminium film.In the etching process, the time of control corrosion reaction rationally is half an hour to one hour, expose the silicon dioxide substrate, at this moment, the carbon nano-tube that distributes at silica surface also partly comes out, and, cover the layer of aluminum metallic film above the unexposed carbon nano-tube part, become the electrode of carbon nano-tube;
5) reprocessing
Remove the self-assembled monolayer above the metallic film, obtain the carbon nano electron device; Used method kept about 10 minutes for being heated to 200 degrees centigrade.
Adopt aluminium be the electrode structure made of electrode material shown in Figure 37,39, Figure 38 be the electrology characteristic curve of electrode structure shown in Figure 37, this carbon nano-tube shows metallicity, plays the connection lead; Figure 40 is the electrology characteristic curve of electrode structure shown in Figure 39, and this carbon nano-tube shows semiconductive, is a field effect transistor.
Embodiment 5, the preparation of employing indirect method are the carbon nano tube device of electrode material with the titanium
The titanium electrode can not form good self-assembled film with stearylmercaptan, and can adopt the indirect method preparation is the carbon nanotube electrode structure of electrode material with the titanium.
The detailed process of preparation is:
1) directly at silicon dioxide substrate surface growth overlength carbon nano pipe;
At silicon dioxide substrate surface growth overlength carbon nano pipe, length is from several microns to about one centimetre; Growth temperature is 800 ~ 1000 degrees centigrade; Growth time is more than 10 minutes; Carbon source is used ethanol; Use hydrogen to be reducing agent; High-purity argon gas is carrier gas.
2) plate the conductive film Titanium
Can adopt hot vapour deposition method to plate one deck titanium film at the silicon dioxide substrate surface that is distributed with carbon nano-tube, the about 60nm of thickness, the thickness of film can change according to the instructions for use of institute's machined electrode, from several nanometers to several micron;
3) depositing metal films
Plate one deck gold film again, the about 20nm of thickness.
4) self-assembled monolayer of formation patterning on metallic film
Adopt the surface scratch method to form the self-assembled monolayer of patterning on the metallic film surface.Used masterplate material is PDMS; There is the metal of self-assembled monolayer in subsequent step, will be protected, can be used as electrode and use; Can obtain different electrode spacings by the spacing that changes the self-assembled monolayer film figure, and then obtain the carbon nanotube field-effect pipe of different channel lengths; The kind of self-assembled monolayer is a stearylmercaptan.
5) first etching
Select the chemical reagent that can play corrosion reaction---the mixed solution of 1M potassium hydroxide and 0.1M potassium thiosulfate for use with golden chromium thin film; in the etching process; the time of control corrosion reaction rationally is half an hour to one hour; at first etch away the gold thin film part that does not have the self-assembled monolayer protection; the time of control corrosion reaction rationally, expose lower conductive film---titanium film.
6) adopt chemical reagent to carry out etching again
The hf etching of employing 1% falls the titanium film portion.The lower conductive film titanium that comes out is carried out etching again, the time of control corrosion reaction rationally is half an hour to one hour, expose the silicon dioxide substrate, also partly come out in the carbon nano-tube that the silicon dioxide substrate surface distributes this moment, and, covering layer of conductive film above the unexposed part carbon nano-tube---titanium film becomes the electrode of carbon nano-tube.
7) reprocessing
Remove the self-assembled monolayer above the gold thin film earlier, used method kept about 10 minutes for being heated to 200 degrees centigrade.
Select the chemical reagent that can play corrosion reaction---the mixed solution of 1M potassium hydroxide and 0.1M potassium thiosulfate again for use with gold thin film, in the etching process, the time of control corrosion reaction rationally is half an hour to one hour, thoroughly etch away the residual gold film on the titanium film, promptly obtaining with the titanium is the electrode structure of electrode material.
Adopt Ti be the electrode structure made of electrode material shown in Figure 43,45, Figure 44 is the electrology characteristic curve of electrode structure shown in Figure 43, this carbon nano-tube shows semiconductive, electrode structure is an ambipolar field effect transistor; Figure 46 is the electrology characteristic curve of electrode structure shown in Figure 45, and this carbon nano-tube shows metallicity, and its IV characteristic shows that this titanium electrode system shows high electric conductivity, plays the effect that connects lead here.
Other, as electrode materials such as conducting polymers such as polythiophene, carbon black, tin oxide, zinc oxide aluminum, ITO conductive films, all can not on electrode material, directly form self-assembled monolayer, also all need to adopt indirect method to prepare carbon nano-tube electron device, its preparation process is identical with said process.
Claims (11)
1, a kind of method for preparing carbon nano-tube electron device comprises the steps:
1) make carbon nano-tube be distributed in insulation dielectric layer substrate surface;
2) in the substrate of insulation dielectric layer, plate metallic film;
3) self-assembled monolayer of formation patterning on metallic film;
4) etching
At different metallic films, select the chemical reagent that can play corrosion reaction for use with metallic film, etch away the metallic film part that does not have the self-assembled monolayer protection, expose the substrate of insulation dielectric layer;
5) reprocessing
Remove the self-assembled monolayer above the metallic film, obtain the carbon nano-tube electron device of metallic film as electrode material.
2, method according to claim 1 is characterized in that: the step 1) carbon nano-tube is distributed in the insulation dielectric layer substrate surface, and location mode can be selected direct surface growth or spin coating, dip-coating mode; The insulation dielectric layer is selected silicon dioxide, zirconium dioxide, hafnium oxide or strontium titanates.
3, method according to claim 1 is characterized in that: step 2) method that plates metallic film is molecular beam epitaxy, hot evaporation, electron beam evaporation plating, magnetron sputtering, chemical plating or electrochemistry plating; The material of metallic film is selected from one or more in gold, silver, copper, platinum, ruthenium, nickel, zinc, palladium, aluminium, the titanium.
4, method according to claim 1 is characterized in that: the method for the self-assembled monolayer of step 3) patterning comprises that micro-contact-printing, nanometer dip in a lithographic method, scan-probe etching method, optical exposure method, surface scratch method; The material selected from mercapto compound of self-assembled monolayer and in the octadecyl phosphoric acid one or more.
5, method according to claim 1 is characterized in that: uv irradiation method, plasma etching method or heating are adopted in the step 5) reprocessing.
6, a kind of method for preparing carbon nano-tube electron device comprises the steps:
1) make carbon nano-tube be distributed in insulation dielectric layer substrate surface;
2) depositing electrically conductive film
In the substrate of insulation dielectric layer, deposit layer of conductive film;
3) depositing metal films
Deposition layer of metal film on conductive film;
4) self-assembled monolayer of formation patterning on metallic film;
5) first etching
At different metallic films, select the chemical reagent that can play corrosion reaction for use with metallic film, etch away the metallic film part that does not have the self-assembled monolayer protection, expose lower conductive film;
6) etching again
Adopt chemical reagent that the lower conductive film that comes out is carried out etching again, the time of control corrosion reaction, expose the substrate of insulation dielectric layer;
7) reprocessing
Remove metallic film and self-assembled monolayer above the conductive film, obtain the carbon nano-tube electron device of conductive film as electrode material.
7, method according to claim 6 is characterized in that: the step 1) carbon nano-tube is distributed in the insulation dielectric layer substrate surface, and location mode can be selected direct surface growth or spin coating, dip-coating mode; The insulation dielectric layer is selected silicon dioxide, zirconium dioxide, hafnium oxide or strontium titanates.
8, method according to claim 6 is characterized in that: step 2) method of depositing electrically conductive film is molecular beam epitaxy, hot evaporation, electron beam evaporation plating, magnetron sputtering, chemical plating or electrochemistry plating; The material of conductive film is selected from metal materials such as titanium, aluminium, conducting polymer composites such as polythiophene, and carbon black, tin oxide, zinc oxide aluminum, ITO conductive film etc.
9, method according to claim 6 is characterized in that: the method that step 3) plates metallic film is molecular beam epitaxy, hot evaporation, electron beam evaporation plating, magnetron sputtering, chemical plating or electrochemistry plating; The material of metallic film is selected from one or more in gold, silver, copper, platinum, ruthenium, nickel, zinc, palladium, aluminium, the titanium.
10, method according to claim 6 is characterized in that: the method for the self-assembled monolayer of step 4) patterning comprises that micro-contact-printing, nanometer dip in a lithographic method, scan-probe etching method, optical exposure method, surface scratch method; The material selected from mercapto compound of self-assembled monolayer and in the octadecyl phosphoric acid one or more.
11, method according to claim 6 is characterized in that: the step 7) reprocessing is removed self-assembled monolayer and is adopted uv irradiation method, plasma etching method or heating; Remove metallic film and adopt chemical etching method.
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