CN104401935B - A kind of method at substrate level direction controllable growth carbon nano-tube bundle - Google Patents
A kind of method at substrate level direction controllable growth carbon nano-tube bundle Download PDFInfo
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Abstract
The invention discloses a kind of method at substrate level direction controllable growth carbon nano-tube bundle, belong to technical field of nanometer material preparation.The method comprises the steps: (1) at substrate surface processes the micro-nano channel of horizontal direction; (2) one end depositing catalytic film bottom micro-nano channel, and carry out graphically to it; (3) the full sacrifice layer of deposition; (4) deposited masking layer, and bottom micro-nano channel the other end top mask layer on etch the passage be communicated with micro-nano channel, removing sacrifice layer, form semi-enclosed micro-nano channel; (5) carbon nano-tube bundle in semi-enclosed micro-nano channel; (6) CNT in removing mask layer, passage and the substrate of carbon nano-tube bundle surrounding thereof, namely obtain the carbon nano-tube bundle with micro-nano channel consistent size in substrate level direction.Its advantage is: the carbon nano-tube bundle that can obtain orientation, size, position controllable precise on substrate level direction; Technical process is simple, is easy to realize, of many uses.
Description
Technical field
The present invention relates to a kind of method at substrate level direction controllable growth carbon nano-tube bundle, belong to technical field of nanometer material preparation.
Background technology
CNT is the body of seamless, the hollow that the graphene sheet layer that formed by carbon atom is curling, and diameter is between a few nanometer to tens nanometer, and length can reach more than some tens of pm.As the monodimension nanometer material of uniqueness, CNT has excellent mechanical property, outstanding electric property and stable chemical property, shows application prospect widely in various fields such as quantum physics research, nanometer electronic device, nano-probe, field emission source, super large capacitor, high strength composite, hydrogen storage materials.In above numerous application, particularly in nanometer electronic device field, the carbon nano-tube bundle that can grow oldered array structure on substrate level direction is the important prerequisite realizing CNT practical application.
All the time, CNT orientations is in the horizontal direction all a great problem of CNT research field.At present, realize CNT horizontal alignment aligning method and mainly contain two classes: a kind of is directly realize the oriented growth in CNT horizontal direction; Another kind the CNT grown is carried out in the horizontal direction rear synthesis arrangement.For the carbon nano-tube oriented growth in horizontal direction, mainly based on chemical vapour deposition technique.Existing research proves, introduces electric field, horizontal growth that magnetic field significantly can promote CNT in chemical vapour deposition technique (CVD) system, but still can deposit the CNT grown in other directions in this approach.In addition, in growth course, control air-flow in CVD system direction and speed can directly prepare the CNT aligned, current this air-flow revulsion prepares the most effective and the most general method of the parallel carbon nano pipe array of overlength on a silicon substrate, but this method can not realize the accurate located growth of CNT.Adopt porous material as template matrix, on matrix, directly growing the carbon nano pipe array with certain orientation by CVD method is also the method preparing oriented growth of carbon nanometer tube extensively adopted at present.But this method mainly exists following defect: one is that through-hole template in horizontal direction prepares poor controllability, although at present can via densities on Control architecture, still cannot accurately control for pore size and arrays of openings; Two is that through-hole template in preparation horizontal direction is very difficult and later stage template process is comparatively complicated.The CNT grown is carried out in the horizontal direction to the method for rear synthesis arrangement, mainly contain mechanical stretching method, flow process, electric field method, magnetic field method and Langmuir-Blodgett (LB) method.Ranking method is synthesized after these, although can in advance by Impurity removals such as catalyst, arrangement mild condition, and easily obtain large-scale, height-oriented carbon nano-tube bundle, but during dispersing Nano carbon tubes bundle will certainly destroying carbon nanometer tube structure and introduce impurity, and these methods also accurately cannot control position and the size of carbon nano-tube bundle.
In sum, prior art cannot realize the carbon nano-tube bundle of size on substrate level direction, position controllable precise, can not meet the demand of most of nanometer electronic device.
Summary of the invention
For existing methodical deficiency, the invention provides the controllable precise that a kind of method at substrate level direction controllable growth carbon nano-tube bundle realizes carbon nano-tube bundle orientation, size and position on substrate.
Object of the present invention is achieved through the following technical solutions:
In a method for substrate level direction controllable growth carbon nano-tube bundle, comprise the steps:
(1) photoetching and etching technics is adopted to process the micro-nano channel of horizontal direction at substrate surface;
(2) one end depositing catalytic film bottom the micro-nano channel adopting thin film deposition processes and photoetching process to process in step (1), and carry out graphically to it;
(3) the full sacrifice layer of deposition in the micro-nano channel after step (2) depositing catalytic film;
(4) the sacrifice layer disposed thereon mask layer adopting thin film deposition processes to deposit in step (3), then on mask layer, etch the passage be communicated with micro-nano channel, and remove sacrifice layer, form semi-enclosed micro-nano channel, described passage is positioned at the top of the other end bottom micro-nano channel;
(5) chemical vapor deposition method carbon nano-tube bundle in semi-enclosed micro-nano channel prepared by step (4) is adopted;
(6) adopt grinding successively, CNT in mask layer above carbon nano-tube bundle that CMP process removing step (5) grows and passage, adopt etching technics to remove the substrate of carbon nano-tube bundle surrounding, namely obtain the carbon nano-tube bundle with micro-nano channel consistent size in substrate level direction.
Said method also comprises the steps: that the substrate after first step (5) being processed soaks more than 10 minutes, then heat cure in thermosetting acrylic resin.
The material of the substrate in described step (1) is exotic material.
Described exotic material is silicon, quartz or aluminium oxide.
Catalytic membrane in described step (2) comprises transition metal layer and alundum (Al2O3) layer from top to bottom successively, and described transition metal layer is Fe layer, Co layer or Ni layer.
The thickness of described alundum (Al2O3) layer is 6 ~ 12 nanometers, and the thickness of transition metal layer is 1 ~ 3 nanometer.
The width of described catalytic membrane is identical with micro-nano channel width, and length is more than 110% of the micro-nano channel degree of depth.
The material of the sacrifice layer in described step (3) is silica, copper or aromatic polyimide.
The composite bed that mask layer in described step (4) is one deck in silicon nitride layer, silicon dioxide layer, layer gold or is made up of which floor.
Described mask layer is the composite bed be made up of silicon nitride layer, silicon oxide layer and layer gold, and described silicon nitride layer is deposited on silicon oxide layer, and silicon oxide layer is deposited in layer gold.
The width of described passage is identical with micro-nano channel width, and length is greater than the width of micro-nano channel and is less than 2/3rds of the length of micro-nano channel.
Substrate level direction carbon nano-tube bundle preparation technology's flow process as shown in Figure 1, specifically comprise the steps:
(1) micro-nano channel 2 photoetching and the substrate 1 surface level direction of etching technics after cleaning-drying processing required size is adopted;
(2) thin film deposition processes is used to deposit the adhesion layer of 6 ~ 12 nanometer thickness and the transition metal layer of 1 ~ 3 nanometer thickness on the surface successively at substrate 1, adhesion layer and transition metal layer composition catalytic membrane 3, adopt photoetching and etching technics that catalytic membrane 3 is graphical, and graphical after catalytic membrane 3 be just positioned at one end bottom micro-nano channel 2;
(3) in substrate 1 micro-nano channel 2, the sacrifice layer 4 of a layer thickness than large 1 ~ 3 micron of micro-nano channel 2 degree of depth is deposited, realize the filling to micro-nano channel 2, adopt the thickness of grinding and the thinning sacrifice layer 4 of CMP process, until plane micro-nano channel 2 removed with the sacrifice layer of exterior domain, and make substrate 1 surface flattening;
(4) adopt thin film deposition processes at sacrifice layer 4 deposited on silicon one deck mask layer 5, photoetching is adopted on mask layer 5, to etch with etching technics the passage 6 be connected with plane micro-nano channel 2, the other end that passage 6 is positioned at above micro-nano channel 2, catalytic membrane 3 place end is corresponding, adopt etching technics to be removed by sacrifice layer 4, form semi-enclosed micro-nano channel 2;
(5) substrate defining semi-enclosed micro-nano channel 2 is put into chemical gas-phase deposition system, adopt chemical vapor deposition method along semi-enclosed micro-nano channel 2 carbon nano-tube, until carbon nano-tube bundle 7 fills full micro-nano channel and passage;
(6) adopt grinding successively, CMP process grinds off CNT above micro-nano channel 2 in mask layer 5 and passage 6, adopt etching technics to remove the substrate of carbon nano-tube bundle surrounding, obtain the carbon nano-tube bundle 8 with micro-nano channel 2 consistent size.
Use substrate to be the substrate that semiconductor technology can be used to process, can also be silicon, germanium silicon, gallium nitride, carborundum, GaAs, silica, zirconia, magnesia or containing the high temperature resistant substrate of these materials.
Use sacrifice layer to be the material being easy to lithography, as silicon, porous silicon, silica, phosphorosilicate glass, polysilicon, metal, high molecular polymer etc.; Meanwhile, the chemical reagent used when must consider removal sacrifice layer when choosing sacrificial layer material and etching gas do not impact mask layer and catalytic membrane.
Use mask layer to be high temperature resistant more than 800 degree and have the thin-film material of excellent mechanical performances, as silicon, silica, silicon nitride, metal and the composite membrane etc. that is made up of these materials; Meanwhile, choosing of mask layer material must consider following two aspects: one is that this mask layer depositing operation does not impact catalytic membrane and sacrifice layer, and two chemical reagent used when being and removing sacrifice layer and etching gas do not affect this mask layer.
Can control carbon nano-tube film size further as required, concrete grammar is: the substrate having grown carbon nano-tube bundle in micro-nano channel is immersed in good fluidity and in curable polymer more than 10 minutes, heat cure, carbon nano-tube bundle is made to form organic whole under the effect of polymer, then grinding, the further thinning micro-nano channel 2 of chemical mechanical polishing technique is used successively, synchronously grind off the unwanted CNT in upper strata, controlled the thickness of carbon nano-tube bundle 8 by the change in depth of micro-nano channel 2.
The present invention is based on existing vertical through hole method.Vertical through hole method adopts microelectronic technique on substrate, process vertical through hole and realize the filling of catalytic membrane in vertical through hole, and recycling chemical vapor deposition method realizes CNT and grows at vertical through hole interior orientation.By the growth course of the position of vertical through hole and catalytic membrane, size, shape restriction carbon nano-tube bundle, finally achieve the controllable growth of substrate vertical direction carbon nano-tube bundle.But, still do not realize the growth of substrate level through hole carbon nano-tube bundle at present.Microelectronic technique and sacrifice layer process combine by the present invention, substrate level direction processes semi-enclosed micro-nano channel and realizes the filling of catalytic membrane in micro-nano channel, utilize the position of micro-nano channel and catalytic membrane, shape, the size restriction growth position of carbon nano-tube bundle, direction and size, the final chemical vapor deposition method that adopts realizes the controllable growth of carbon nano-tube bundle on substrate level direction.
The present invention processes micro-nano channel in the position that substrate is corresponding according to demand, and the position of micro-nano channel has has just regulated and controled CNT in on-chip position, the size of micro-nano channel determines the size of CNT, the position of catalytic membrane determines the direction of growth of CNT, that is according to the demand of producing, the CNT in required size and direction can be grown in the position that substrate is specified.
The invention has the beneficial effects as follows: the carbon nano-tube bundle that orientation, size, position controllable precise 1) can be obtained on substrate level direction; 2) adopt technique to be microelectronic technique and the micro-electromechanical processing technology of standard, be beneficial to and realize based on the integrated nanometer electronic device of CNT; 3) technical process is simple, is easy to realize, and is easy to integrated, of many uses.
Accompanying drawing explanation
Fig. 1 is substrate level direction of the present invention carbon nano-tube bundle preparation method flow chart;
Fig. 2 is embodiment of the present invention result of implementation schematic diagram;
Wherein, 1-substrate, 2-micro-nano channel, 3-catalytic membrane, 4-sacrifice layer, 5-mask layer, 6-passage, 7-carbon nano-tube bundle, 8-is filled in the carbon nano-tube bundle in micro-nano channel.
Detailed description of the invention
Be further described technical scheme of the present invention below in conjunction with accompanying drawing and specific embodiment, following examples do not form limitation of the invention.
Embodiment 1
(1) a slice silicon chip 1 is prepared, adopt conventional semiconductor cleaning to clean, dry, use photoetching process and ion reaction etching technique to need the position of carbon nanotube film to process long 10 microns at silicon chip surface, wide 2 microns, the horizontal direction micro-nano channel 2 of dark 2 microns;
(2) adopt sol evenning machine at silicon chip 1 surperficial spin coating one deck AZ4620 photoresist, thickness is 3 microns, exposure imaging exposes catalytic membrane deposition window, use electron beam evaporation process on silicon chip surface, deposit the alundum (Al2O3) layer of 6 nanometer thickness and the Co layer composition catalytic membrane 3 of 1 nanometer thickness successively, remove photoresist, catalytic membrane on photoresist is removed thereupon together, to stay in micro-nano channel 2 graphical after catalytic membrane 3, catalytic membrane be of a size of wide 2 microns, long 2.2 microns;
(3) sol evenning machine is adopted to be that the aromatic polyimide of 2 microns is as sacrifice layer 4 in the surperficial spin coating a layer thickness of silicon chip 1, micro-nano channel 2 is filled up, grinding and mechanical polishing process is used to be removed by the aromatic polyimide outside plane micro-nano channel successively, and leveling silicon chip 1;
(4) sputtering technology is adopted to deposit 200nm thick Au layer, the thick Si of 3um successively on silicon chip 1 surface
3n
4layer composition composite masking layer, covers above aromatic polyimide; Adopt the mask layer 5 above ion beam etch process etching micro-nano channel 2, form the passage 6 be connected with micro-nano channel, passage 6 is positioned at above micro-nano channel 2, the other end that catalytic membrane 3 place end is corresponding, be of a size of wide 2 microns, grow 2.2 microns; Silicon chip 1 entirety to be immersed in the acetone of 60 DEG C 2 hours, to remove the aromatic polyimide in micro-nano channel 2, form semienclosed micro-nano channel;
(5) silicon chip 1 etching passage is put into chemical gas-phase deposition system, pass into the argon gas of 900sccm and the hydrogen of 100sccm, silicon chip be heated to 700 DEG C simultaneously and keep 15 minutes; Be filled with the acetylene gas of 6sccm in the reactor, the flow of argon gas and hydrogen be adjusted to 500sccm simultaneously, carry out the growth of CNT in micro-nano channel; Carbon nano-tube bundle closes acetylene gas grow 15 minutes in passage after, and argon gas is adjusted to 900sccm, and hydrogen is adjusted to 100sccm, stop heating simultaneously, take out silicon chip 1 under naturally cooling to room temperature, so far, in micro-nano channel 2 and passage 6, fill full carbon nano-tube bundle 7;
(6) employing grinding and chemical mechanical polishing method grind off the CNT in mask layer 5 and passage 6 successively, expose CNT, adopt etching technics by the wafer thinning 2um outside carbon nano-tube bundle, obtain consistent with micro-nano channel 2, long 10 microns, wide 2 microns, the carbon nano-tube bundle 8(of thick 2 microns forms the result schematic diagram of carbon nano-tube bundle as shown in Figure 2 on silicon wafer horizontal direction).
Embodiment 2
(1) a slice quartz plate 1 is prepared, adopt conventional semiconductor cleaning to clean, dry, use photoetching process and ion reaction etching technique to need the position of carbon nano-tube bundle to process long 10 microns on quartz plate surface, wide 2 microns, the horizontal direction micro-nano channel 2 of dark 2 microns;
(2) adopt sol evenning machine at quartz plate 1 surperficial spin coating one deck AZ4620 photoresist, thickness is 3 microns, exposure imaging exposes catalytic membrane deposition window, electron beam evaporation process is used to deposit the alundum (Al2O3) layer of 10 nanometer thickness and the Fe layer composition catalytic membrane 3 of 2 nanometer thickness on the surface successively at quartz plate, remove photoresist, catalytic membrane on photoresist is removed thereupon together, to stay in micro-nano channel 2 graphical after catalytic membrane 3, catalytic membrane be of a size of long 2.3 microns, wide 2 microns;
(3) adopt electroplating technology quartz plate 1 surface deposition a layer thickness be the copper film of 2 microns as sacrifice layer 4, micro-nano channel 2 is filled up, uses grinding and mechanical polishing process by the copper removal outside plane micro-nano channel successively, and leveling quartz plate 1;
(4) sputtering technology is adopted to deposit the thick SiO of 2um successively on quartz plate 1 surface
2layer, the thick Si of 2um
3n
4layer composition composite masking layer 5, covers above copper sacrifice layer; Adopt the mask layer 5 above ion beam etch process etching micro-nano channel 2, form the passage 6 be connected with micro-nano channel, passage 6 is positioned at above micro-nano channel 2, the other end that catalytic membrane 3 place end is corresponding, be of a size of wide 2 microns, grow 3 microns; Quartz plate 1 entirety to be immersed in copper corrosion liquid ferric trichloride 2 hours, to remove the copper in micro-nano channel 2, form semienclosed micro-nano channel;
(5) quartz plate 1 etching passage is put into chemical gas-phase deposition system, pass into the argon gas of 900sccm and the hydrogen of 100sccm, quartz plate be heated to 700 DEG C simultaneously and keep 15 minutes; Be filled with the acetylene gas of 6sccm in the reactor, the flow of argon gas and hydrogen be adjusted to 500sccm simultaneously, carry out the growth of CNT in micro-nano channel; Carbon nano-tube bundle closes acetylene gas grow 15 minutes in passage after, argon gas is adjusted to 900sccm, hydrogen is adjusted to 100sccm, stop heating simultaneously, quartz plate 1 is taken out under naturally cooling to room temperature, so far, full carbon nano-tube bundle 7 is filled in micro-nano channel 2 and passage 6, the quartz plate having grown carbon nano-tube bundle to be immersed in thermosetting acrylic resin 10 minutes, take out, put into baking oven 120 DEG C of heat cures 30 minutes, make CNT bonding one-tenth organic whole under the effect of acrylic resin, be conducive to follow-up attrition process;
(6) CNT in adopt grinding and chemical mechanical polishing method to grind off successively acrylic resin, mask layer 5 and passage 6 that upper strata is cured, expose CNT, adopt etching technics by thinning for the quartz plate outside carbon nano-tube bundle 2um, obtain consistent with micro-nano channel 2, long 10 microns, wide 2 microns, the carbon nano-tube bundle 8 of thick 2 microns.
Embodiment 3
(1) a slice alumina wafer 1 is prepared, adopt conventional semiconductor cleaning to clean, dry, use photoetching process and ion reaction etching technique to need the position of carbon nano-tube bundle to process long 10 microns at alumina surface, wide 2 microns, the horizontal direction micro-nano channel 2 of dark 2 microns;
(2) adopt sol evenning machine at alumina wafer 1 surperficial spin coating one deck AZ4620 photoresist, thickness is 3 microns, exposure imaging exposes catalytic membrane deposition window, electron beam evaporation process is used to deposit the alundum (Al2O3) layer of 12 nanometer thickness and the Ni layer composition catalytic membrane 3 of 3 nanometer thickness on the surface successively at alumina wafer, remove photoresist, catalytic membrane on photoresist is removed thereupon together, to stay in micro-nano channel 2 graphical after catalytic membrane 3, catalytic membrane be of a size of long 2.4 microns, wide 2 microns;
(3) pecvd process is adopted to be that the silicon dioxide film of 3 microns is as sacrifice layer 4 in alumina wafer 1 surface deposition a layer thickness, micro-nano channel 2 is filled up, grinding and mechanical polishing process is used to be removed by the silica outside plane micro-nano channel successively, and leveling alumina wafer 1;
(4) sputtering technology is adopted to deposit 200nm thick Au layer, the thick SiO of 2um successively on alumina wafer 1 surface
2layer, the thick Si of 2um
3n
4layer composition composite masking layer, covers above silicon dioxide sacrificial layer; Adopt the mask layer 5 above ion beam etch process etching micro-nano channel 2, form the passage 6 be connected with micro-nano channel, passage 6 is positioned at above micro-nano channel 2, the other end that catalytic membrane 3 place end is corresponding, be of a size of wide 2 microns, grow 4 microns; Adopt reactive ion etching process silicon dioxide sacrificial layer to be removed, form semienclosed micro-nano channel;
(5) alumina wafer 1 etching passage is put into chemical gas-phase deposition system, pass into the argon gas of 900sccm and the hydrogen of 100sccm, alumina wafer be heated to 700 DEG C simultaneously and keep 15 minutes; Be filled with the acetylene gas of 6sccm in the reactor, the flow of argon gas and hydrogen be adjusted to 500sccm simultaneously, carry out the growth of CNT in micro-nano channel; Carbon nano-tube bundle closes acetylene gas grow 15 minutes in passage after, argon gas is adjusted to 900sccm, hydrogen is adjusted to 100sccm, stop heating simultaneously, alumina wafer 1 is taken out under naturally cooling to room temperature, so far, full carbon nano-tube bundle 7 is filled in micro-nano channel 2 and passage 6, the quartz plate having grown carbon nano-tube bundle to be immersed in thermosetting acrylic resin 20 minutes, take out, put into baking oven 120 DEG C of heat cures 30 minutes, make CNT bonding one-tenth organic whole under the effect of acrylic resin, be conducive to follow-up attrition process;
(6) employing grinding and chemical mechanical polishing method grind off the CNT in mask layer 5 and passage 6 successively, expose CNT, adopt etching technics by thinning for the alumina wafer outside carbon nano-tube bundle 2um, obtain consistent with micro-nano channel 2, long 10 microns, wide 2 microns, the carbon nano-tube bundle 8 of thick 2 microns.
Embodiment 4
(1) a slice alumina wafer 1 is prepared, adopt conventional semiconductor cleaning to clean, dry, use photoetching process and ion reaction etching technique to need the position of carbon nano-tube bundle to process long 10 microns at alumina surface, wide 2 microns, the horizontal direction micro-nano channel 2 of dark 2 microns;
(2) adopt sol evenning machine at alumina wafer 1 surperficial spin coating one deck AZ4620 photoresist, thickness is 3 microns, exposure imaging exposes catalytic membrane deposition window, electron beam evaporation process is used to deposit the alundum (Al2O3) layer of 12 nanometer thickness and the Ni layer composition catalytic membrane 3 of 3 nanometer thickness on the surface successively at alumina wafer, remove photoresist, catalytic membrane on photoresist is removed thereupon together, to stay in micro-nano channel 2 graphical after catalytic membrane 3, catalytic membrane be of a size of long 2.4 microns, wide 2 microns;
(3) pecvd process is adopted to be that the silicon dioxide film of 3 microns is as sacrifice layer 4 in alumina wafer 1 surface deposition a layer thickness, micro-nano channel 2 is filled up, grinding and mechanical polishing process is used to be removed by the silica outside plane micro-nano channel successively, and leveling alumina wafer 1;
(4) adopt sputtering technology at the thick Si of alumina wafer 1 surface deposition 3um
3n
4mask layer, covers above silicon dioxide sacrificial layer; Adopt the mask layer 5 above ion beam etch process etching micro-nano channel 2, form the passage 6 be connected with micro-nano channel, passage 6 is positioned at above micro-nano channel 2, the other end that catalytic membrane 3 place end is corresponding, be of a size of wide 2 microns, grow 4 microns; Adopt reactive ion etching process silicon dioxide sacrificial layer to be removed, form semienclosed micro-nano channel;
(5) alumina wafer 1 etching passage is put into chemical gas-phase deposition system, pass into the argon gas of 900sccm and the hydrogen of 100sccm, alumina wafer be heated to 700 DEG C simultaneously and keep 15 minutes; Be filled with the acetylene gas of 6sccm in the reactor, the flow of argon gas and hydrogen be adjusted to 500sccm simultaneously, carry out the growth of CNT in micro-nano channel; Carbon nano-tube bundle closes acetylene gas grow 15 minutes in passage after, and argon gas is adjusted to 900sccm, and hydrogen is adjusted to 100sccm, stop heating simultaneously, take out alumina wafer 1 under naturally cooling to room temperature, so far, in micro-nano channel 2 and passage 6, fill full carbon nano-tube bundle 7;
(6) adopt grinding and chemical mechanical polishing method to grind off CNT in mask layer 5 and passage 6 successively, expose CNT, obtain consistent with micro-nano channel 2, grow 10 microns, wide 2 microns, the carbon nano-tube bundle 8 of thick 2 microns.
Embodiment 5
(1) a slice alumina wafer 1 is prepared, adopt conventional semiconductor cleaning to clean, dry, use photoetching process and ion reaction etching technique to need the position of carbon nano-tube bundle to process long 10 microns at alumina surface, wide 2 microns, the horizontal direction micro-nano channel 2 of dark 2 microns;
(2) adopt sol evenning machine at alumina wafer 1 surperficial spin coating one deck AZ4620 photoresist, thickness is 3 microns, exposure imaging exposes catalytic membrane deposition window, electron beam evaporation process is used to deposit the alundum (Al2O3) layer of 12 nanometer thickness and the Ni layer composition catalytic membrane 3 of 3 nanometer thickness on the surface successively at alumina wafer, remove photoresist, catalytic membrane on photoresist is removed thereupon together, to stay in micro-nano channel 2 graphical after catalytic membrane 3, catalytic membrane be of a size of long 2.4 microns, wide 2 microns;
(3) adopt electroplating technology alumina wafer 1 surface deposition a layer thickness be the copper film of 2 microns as sacrifice layer 4, micro-nano channel 2 is filled up, uses grinding and mechanical polishing process by the copper removal outside plane micro-nano channel successively, and leveling alumina wafer 1;
(4) adopt sputtering technology at the thick SiO of alumina wafer 1 surface deposition 3um
2mask layer, covers above copper sacrifice layer; Adopt the mask layer 5 above ion beam etch process etching micro-nano channel 2, form the passage 6 be connected with micro-nano channel, passage 6 is positioned at above micro-nano channel 2, the other end that catalytic membrane 3 place end is corresponding, be of a size of wide 2 microns, grow 4 microns; Alumina wafer 1 entirety to be immersed in copper corrosion liquid ferric trichloride 1 hour, to remove the copper in micro-nano channel 2, form semienclosed micro-nano channel;
(5) alumina wafer 1 etching passage is put into chemical gas-phase deposition system, pass into the argon gas of 900sccm and the hydrogen of 100sccm, alumina wafer be heated to 700 DEG C simultaneously and keep 15 minutes; Be filled with the acetylene gas of 6sccm in the reactor, the flow of argon gas and hydrogen be adjusted to 500sccm simultaneously, carry out the growth of CNT in micro-nano channel; Carbon nano-tube bundle closes acetylene gas grow 15 minutes in passage after, and argon gas is adjusted to 900sccm, and hydrogen is adjusted to 100sccm, stop heating simultaneously, take out alumina wafer 1 under naturally cooling to room temperature, so far, in micro-nano channel 2 and passage 6, fill full carbon nano-tube bundle 7;
(6) adopt grinding and chemical mechanical polishing method to grind off CNT in mask layer 5 and passage 6 successively, expose CNT, obtain consistent with micro-nano channel 2, grow 10 microns, wide 2 microns, the carbon nano-tube bundle 8 of thick 2 microns.
Embodiment 6
(1) a slice alumina wafer 1 is prepared, adopt conventional semiconductor cleaning to clean, dry, use photoetching process and ion reaction etching technique to need the position of carbon nano-tube bundle to process long 10 microns at alumina surface, wide 2 microns, the horizontal direction micro-nano channel 2 of dark 2 microns;
(2) adopt sol evenning machine at alumina wafer 1 surperficial spin coating one deck AZ4620 photoresist, thickness is 3 microns, exposure imaging exposes catalytic membrane deposition window, electron beam evaporation process is used to deposit the alundum (Al2O3) layer of 12 nanometer thickness and the Ni layer composition catalytic membrane 3 of 3 nanometer thickness on the surface successively at alumina wafer, remove photoresist, catalytic membrane on photoresist is removed thereupon together, to stay in micro-nano channel 2 graphical after catalytic membrane 3, catalytic membrane be of a size of long 2.4 microns, wide 2 microns;
(3) pecvd process is adopted to be that the silicon dioxide film of 3 microns is as sacrifice layer 4 in alumina wafer 1 surface deposition a layer thickness, micro-nano channel 2 is filled up, grinding and mechanical polishing process is used to be removed by the silica outside plane micro-nano channel successively, and leveling alumina wafer 1;
(4) adopt sputtering technology at alumina wafer 1 surface deposition 2um thick Au layer composition composite masking layer, cover above silicon dioxide sacrificial layer; Adopt the mask layer 5 above ion beam etch process etching micro-nano channel 2, form the passage 6 be connected with micro-nano channel, passage 6 is positioned at above micro-nano channel 2, the other end that catalytic membrane 3 place end is corresponding, be of a size of wide 2 microns, grow 4 microns; Adopt reactive ion etching process silicon dioxide sacrificial layer to be removed, form semienclosed micro-nano channel;
(5) alumina wafer 1 etching passage is put into chemical gas-phase deposition system, pass into the argon gas of 900sccm and the hydrogen of 100sccm, alumina wafer be heated to 700 DEG C simultaneously and keep 15 minutes; Be filled with the acetylene gas of 6sccm in the reactor, the flow of argon gas and hydrogen be adjusted to 500sccm simultaneously, carry out the growth of CNT in micro-nano channel; Carbon nano-tube bundle closes acetylene gas grow 15 minutes in passage after, and argon gas is adjusted to 900sccm, and hydrogen is adjusted to 100sccm, stop heating simultaneously, take out alumina wafer 1 under naturally cooling to room temperature, so far, in micro-nano channel 2 and passage 6, fill full carbon nano-tube bundle 7;
(6) adopt grinding and chemical mechanical polishing method to grind off CNT in mask layer 5 and passage 6 successively, expose CNT, obtain consistent with micro-nano channel 2, grow 10 microns, wide 2 microns, the carbon nano-tube bundle 8 of thick 2 microns.
Claims (10)
1., in a method for substrate level direction controllable growth carbon nano-tube bundle, it is characterized in that comprising the steps:
(1) photoetching and etching technics is adopted to process the micro-nano channel of horizontal direction at substrate surface;
(2) one end depositing catalytic film bottom the micro-nano channel adopting thin film deposition processes and photoetching process to process in step (1), and carry out graphically to it;
(3) the full sacrifice layer of deposition in the micro-nano channel after step (2) depositing catalytic film;
(4) the sacrificial layer surface deposited masking layer adopting thin film deposition processes to deposit in step (3), then etches the passage be communicated with micro-nano channel, and removes sacrifice layer, form semi-enclosed micro-nano channel on mask layer; Described passage is positioned at the top of the other end bottom micro-nano channel;
(5) chemical vapor deposition method carbon nano-tube bundle in semi-enclosed micro-nano channel prepared by step (4) is adopted;
(6) adopt grinding successively, the mask layer above carbon nano-tube bundle that CMP process removing step (5) grows and the CNT in passage, adopt etching technics to remove the substrate of carbon nano-tube bundle surrounding, namely obtain the carbon nano-tube bundle with micro-nano channel consistent size in substrate level direction.
2. a kind of method at substrate level direction controllable growth carbon nano-tube bundle according to claim 1, it is characterized in that: before step (6), also comprise the steps: that the substrate after first step (5) being processed soaks more than 10 minutes, then heat cure in thermosetting acrylic resin.
3. a kind of method at substrate level direction controllable growth carbon nano-tube bundle according to claim 1 or 2, is characterized in that: the material of the substrate in described step (1) is exotic material.
4. a kind of method at substrate level direction controllable growth carbon nano-tube bundle according to claim 3, is characterized in that: described exotic material is silicon, quartz or aluminium oxide.
5. a kind of method at substrate level direction controllable growth carbon nano-tube bundle according to claim 1 or 2, it is characterized in that: the catalytic membrane in described step (2) comprises transition metal layer and alundum (Al2O3) layer from top to bottom successively, described transition metal layer is Fe layer, Co layer or Ni layer; The width of described catalytic membrane is identical with micro-nano channel width, and length is more than 110% of the micro-nano channel degree of depth.
6. a kind of method at substrate level direction controllable growth carbon nano-tube bundle according to claim 5, it is characterized in that: the thickness of described alundum (Al2O3) layer is 6 ~ 12 nanometers, the thickness of transition metal layer is 1 ~ 3 nanometer.
7. a kind of method at substrate level direction controllable growth carbon nano-tube bundle according to claim 1 or 2, is characterized in that: the material of the sacrifice layer in described step (3) is silica, copper or aromatic polyimide.
8. a kind of method at substrate level direction controllable growth carbon nano-tube bundle according to claim 1 or 2, is characterized in that: the composite bed that the mask layer in described step (4) is one deck in silicon nitride layer, silicon dioxide layer, layer gold or is made up of which floor.
9. a kind of method at substrate level direction controllable growth carbon nano-tube bundle according to claim 8, it is characterized in that: described mask layer is the composite bed be made up of silicon nitride layer, silicon oxide layer and layer gold, described silicon nitride layer is deposited on silicon oxide layer, and silicon oxide layer is deposited in layer gold.
10. a kind of method at substrate level direction controllable growth carbon nano-tube bundle according to claim 1 or 2, it is characterized in that: the width of described passage is identical with micro-nano channel width, length is greater than the width of micro-nano channel and is less than 2/3rds of the length of micro-nano channel.
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| CN103265009A (en) * | 2013-05-24 | 2013-08-28 | 厦门大学 | Preparation method of horizontal array carbon nano tube |
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| JP2008230957A (en) * | 2007-02-20 | 2008-10-02 | National Institute Of Advanced Industrial & Technology | Carbon nanotube film structure and its production method |
| US20130181352A1 (en) * | 2012-01-16 | 2013-07-18 | Industry-Academic Cooperation Foundation at NamSeoul Unversity | Method of Growing Carbon Nanotubes Laterally, and Lateral Interconnections and Effect Transistor Using the Same |
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| CN1334234A (en) * | 2000-07-18 | 2002-02-06 | Lg电子株式会社 | Method of horizontal growth of carbon nanotube and field effect transistor using carbon nanotube |
| CN1660696A (en) * | 2004-02-25 | 2005-08-31 | 三星电子株式会社 | Method of horizontally growing carbon nanotubes and device having the same |
| CN1907845A (en) * | 2005-08-05 | 2007-02-07 | 鸿富锦精密工业（深圳）有限公司 | Carbon nano-tube preparation method and apparatus |
| CN101104509A (en) * | 2007-08-20 | 2008-01-16 | 中山大学 | Method for preparing single nano material in pore space structure |
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