CN100413010C - Nano carbon tube based field emitting cathode and its preparing method - Google Patents
Nano carbon tube based field emitting cathode and its preparing method Download PDFInfo
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- CN100413010C CN100413010C CNB2004100095101A CN200410009510A CN100413010C CN 100413010 C CN100413010 C CN 100413010C CN B2004100095101 A CNB2004100095101 A CN B2004100095101A CN 200410009510 A CN200410009510 A CN 200410009510A CN 100413010 C CN100413010 C CN 100413010C
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Abstract
The present invention discloses a field emission cathode based on nanometer carbon tubes and a manufacture method of the field emission cathode. The nanometer carbon tubes are ranged and distributed on a pole plate of the field emission cathode in a lying mode. The manufacture method comprises the steps that the nanometer carbon tubes are placed in alcohol or other solvent, stirred and dispersed to obtain solution; the obtained solution is directly dropped on the pole plate of the cathode; the pole plate of the field emission cathode, which has the nanometer carbon tube solution, is naturally dried. After the nanometer carbon tubes arranged on the pole plate of the field emission cathode of the present invention are laid flatly, the manufacture technology is greatly simplified, and the cost is greatly reduced. The field emission cathode of the present invention avoids the difficulty of uprightly ranging and distributing the nanometer carbon tubes, the production cost is greatly reduced, and the performance is enhanced.
Description
Technical field
The present invention relates to a kind of field-transmitting cathode based on CNT (carbon nano-tube) and preparation method thereof.
Background technology
Preparing field-transmitting cathode and make flat-panel monitor with CNT (carbon nano-tube) is a up-and-coming technical field.The draw ratio of carbon nano-tube is big, the top radius of curvature operating time little, emitting electrons is long, thereby is good display basic material.The geometry comparison rule of traditional carbon nano-tube compares homogeneous along the diameter distribution of tube axis direction.So the mechanism of its field-causing electron emission is mainly, and launch on the top, the contribution of side is very little, does not give full play to effective usable floor area of nanotube.Utilize all the time CNT (carbon nano-tube) prepare field-transmitting cathode all be the top emission that utilizes the carbon pipe [Walt A.de Heer et al, Science 270 (1995) 1179; Jean DIJON-LETI/CEAGrenoble, Reported at MINATEC 2003], this just need be with CNT (carbon nano-tube) perpendicular to the cathode plate planar alignment.The upright carbon nanotube film of direct growth is a kind of effective ways on cathode plane, but because conditions such as carbon pipe growth needs high temperature and chemical reaction, direct growth target material itself has on the one hand proposed extra demand, also limit the condition of carbon pipe growth on the other hand, thereby can not control the quality of carbon pipe well.The carbon pipe for preparing is assembled on the cathode plate also is difficult at present realizing having the good carbon pipe array of uprightly arranging that contacts and have the good field electron emission capability with electrode.
Summary of the invention
At the existing problem and shortage of the field-transmitting cathode of above-mentioned existing CNT (carbon nano-tube), the purpose of this invention is to provide a kind of CNT (carbon nano-tube) lie low on the field-transmitting cathode pole plate based on field-transmitting cathode of CNT (carbon nano-tube) and preparation method thereof.
The present invention is achieved in that a kind of field-transmitting cathode based on CNT (carbon nano-tube), and described CNT (carbon nano-tube) is arranged on the described field-transmitting cathode pole plate in the mode that lies low.
Further, described CNT (carbon nano-tube) inside is filled with metal or metal oxide particle, and described particle makes the outer wall of described CNT (carbon nano-tube) constitute a plurality of how much projections.
A kind of preparation method of field-transmitting cathode may further comprise the steps:
(1) described CNT (carbon nano-tube) is placed in alcohol or other solvents, dispersed with stirring is made solution;
(2) solution in the step (1) is directly dripped on the described cathode plate;
(3) the described cathode plate that CNT (carbon nano-tube) solution arranged dried naturally get final product.
Further, the dispersing nanometer carbon pipe in the above-mentioned steps (1) can also be ultrasonic aid dispersion.
Further, can also solution be dripped on the described cathode plate with the rotary plating method in the above-mentioned steps (2).
A kind of preparation method of field-transmitting cathode may further comprise the steps:
(1) 1.8g Al
2O
3Add in the 20ml absolute ethyl alcohol, stir fast; Add positive tetraethyl orthosilicate of 2.08g and 20ml water again; After treating the abundant hydrolysis of positive tetraethyl orthosilicate, add 1-5g Fe
2(SO
4)
35H
2O; After treating that colloidal sol forms, adopt the method for rotation coating technique or infiltration naturally on cathode plate, to make the silicon oxide film that comprises catalyst granules;
(2) ferrocene of 1-10g is dissolved in the 200-400ml acetonitrile obtains ferrocene/acetonitrile solution;
(3) cathode plate that step (1) is made is in 750 ℃ of argon gas roasting 30-45 minute; Be warming up to 930 ℃-950 ℃ by 25 ℃/min, this moment at the heating furnace inlet end with syringe to the cathode plate ferrocene/acetonitrile solution of injecting step (2) preparation off and on;
(4) the cathode plate natural cooling that step (3) is made gets final product.
Further, the time of staying of the volume of the injection solution in the above-mentioned steps (3), the time interval between every double injection and per injection solution can change, with the size interval parameter of the length, distribution density and the CNT (carbon nano-tube) inner stuffing that change CNT (carbon nano-tube).
Further, above-mentioned cathode plate can be conductive silicon chip.
The present invention adopts lie low arrangement on the field-transmitting cathode pole plate of CNT (carbon nano-tube), field-transmitting cathode performance of the present invention is significantly improved than the performance that uprightly is arranged in the field-transmitting cathode of making on the pole plate with CNT (carbon nano-tube) of the same race, be embodied as cut-in voltage and reduce, field enhancement factor increases.Because CNT (carbon nano-tube) is top emission electronic not only, and its side also has the side emission ability.Because the carbon nano-tube that lies low has identical height substantially, most carbon nano-tube all can participate in an electronics emission.Improve emission current on the one hand, also improved the launch stability energy of prepared negative electrode on the other hand.After CNT (carbon nano-tube) on the field-transmitting cathode pole plate of the present invention lies low, its processing technology will be simplified greatly, and cost also greatly reduces.Field-transmitting cathode of the present invention avoided uprightly the arranging difficulty of carbon pipe greatly reduces production cost and has improved performance.
Description of drawings
Below in conjunction with accompanying drawing, the present invention is made detailed description.
Fig. 1 is the electron scanning micrograph schematic diagram of field-transmitting cathode of the present invention;
Fig. 2 is the transmission electron microscope photo schematic diagram of CNT (carbon nano-tube) of the present invention;
Fig. 3 is the comparison schematic diagram of characteristic and other The Characteristics of Field Emitter Array of field-transmitting cathode of the present invention;
Fig. 4 is the top of carbon nano-tube of the present invention and the potential barrier curve of side emission electronics.
Embodiment
CNT (carbon nano-tube) of the present invention is arranged on the described field-transmitting cathode pole plate in the mode that lies low.CNT (carbon nano-tube) of the present invention inside is filled with metal or metal oxide particle, and the particle of filling makes the outer wall of CNT (carbon nano-tube) constitute a plurality of how much projections.Wherein, CNT (carbon nano-tube) can be made by following steps:
(1) select metallic catalyst according to the target filler, preparation is used to generate the mixed solution of metallic catalyst/carrier;
(2) solution with step (1) preparation gained prepares film on substrate;
(3) substrate that will be covered with film is in air or have in the environment of oxygen heat treatment make film be set on the substrate and form metallic catalyst/carrier laminated film;
(4) substrate that will be covered with metallic catalyst/carrier laminated film is placed on heating in the heating furnace; atmosphere is the gaseous mixture of inert gas or hydrogen and inert gas; introduce simultaneously carbon source by phased manner; and introduce doped chemical nitrogen, boron, phosphorus or sulphur simultaneously; introducing the amount and the time interval of carbon source regulates according to the length of the filler spacing in the needed nanotube and nanotube and filler; reaction is cooled to normal temperature and gets final product after finishing under inert gas shielding.The inert gas here is argon gas preferably.The CNT (carbon nano-tube) structure as shown in Figure 2.Among the figure, filler is a ferric oxide particles.
Here, the invention provides the process of two kinds of field-transmitting cathodes:
(1) CNT (carbon nano-tube) that said method is made is placed in the alcohol (or other solvent) and disperses.Available dispersed with stirring, also available ultrasonic aid dispersion.
(2) scattered carbon pipe solution is dripped on the cathode plate.Can directly drip also available rotary plating (spincoating) method.If the cathode plate corrosion of not being afraid of above-mentioned solution, reintroduce (dip coating) after also pole plate can being immersed solution, but also the carbon periosteum will be arranged at the side and the back side of pole plate like this.
(3) pole plate is dried the film of just having made the carbon pipe that lies low.
Can come into operation after test performance is qualified.This preparation method is that the carbon pipe that length is good is assembled into the method on the pole plate.
(1) with 1.8g Al
2O
3Add in the 20ml absolute ethyl alcohol, stir fast; Add positive tetraethyl orthosilicate of 2.08g and 20ml water; After treating the abundant hydrolysis of positive tetraethyl orthosilicate, add Fe
2(SO
4)
35H
2O, consumption are 1-5g; After treating that colloidal sol forms, adopt the method for rotation coating technique or infiltration naturally upward to make the silicon oxide film that comprises catalyst granules at conductive silicon chip substrate (or other selected cathode plate).
(2) ferrocene about 1-10g is dissolved in the 200-400ml acetonitrile.
(3) silicon chip (or other cathode plate) that will apply catalyst film is in 750 ℃ of argon gas roasting 30-45 minute; Be warming up to 930 ℃-950 ℃ by 25 ℃/min, feed the ferrocene/acetonitrile solution of step (2) preparation this moment at the heating furnace inlet end with syringe.During injection, can change the technological parameters such as the time of staying of volume, the time interval between every double injection and the per injection solution of injection solution.The purpose that changes process conditions is length, the distribution density of nanotube and the parameter such as size interval of carbon pipe inner stuffing that changes CNT (carbon nano-tube).
(4) will grow good cathode plate cooling.This method is the method for directly growing on pole plate.
Can come into operation after test performance is qualified.Step in this method (1) and (2) are interchangeable.Here as long as guarantee its solution concentration, not to the solution quantitative limitation.
Field-transmitting cathode pole plate of the present invention as shown in Figure 1.
As shown in Figure 3, field-transmitting cathode performance of the present invention is several significantly better than other.Among the figure, I is the characteristic of the packless CNT (carbon nano-tube) negative electrode of uprightly arranging; II is the characteristic of the CNT (carbon nano-tube) negative electrode that filling is arranged of uprightly arranging; III is the characteristic of the CNT (carbon nano-tube) negative electrode that filling is arranged of arranging of lying low of the present invention.
As shown in Figure 4, be the top of the CNT (carbon nano-tube) of the present invention of Theoretical Calculation and the potential barrier curve chart of side emission electronics.There is projection on CNT (carbon nano-tube) of the present invention surface, and then its side direction potential barrier is lower, and side emission efficient is than top-emission efficient height.Curve is what calculate by first principle among the figure.
Claims (6)
1. the field-transmitting cathode based on CNT (carbon nano-tube) is characterized in that, described CNT (carbon nano-tube) is arranged on the described field-transmitting cathode pole plate in the mode that lies low.
2. the field-transmitting cathode based on CNT (carbon nano-tube) as claimed in claim 1 is characterized in that, described CNT (carbon nano-tube) inside is filled with metal or metal oxide particle, and described particle makes the outer wall of described CNT (carbon nano-tube) constitute a plurality of how much projections.
3. the preparation method of the field-transmitting cathode in the claim 2 is characterized in that the CNT (carbon nano-tube) that filling is arranged that will prepare in advance is assembled on the pole plate with lying low, may further comprise the steps:
(1) described CNT (carbon nano-tube) is placed in alcohol or other solvents, dispersed with stirring or ultrasonic aid dispersion are made solution;
(2) solution in the step (1) is directly dripped on the described cathode plate or adopt the rotary plating method to drip on the described cathode plate;
(3) the described cathode plate that CNT (carbon nano-tube) solution arranged dried naturally get final product.
4. the preparation method of the field-transmitting cathode in the claim 2 is characterized in that the CNT (carbon nano-tube) that filling is arranged that directly growth lies low on pole plate, may further comprise the steps:
(1) 1.8g Al
2O
3Add in the 20ml absolute ethyl alcohol, stir fast; Add positive tetraethyl orthosilicate of 2.08g and 20ml water again; After treating the abundant hydrolysis of positive tetraethyl orthosilicate, add 1-5g Fe
2(SO
4)
35H
2O; After treating that colloidal sol forms, adopt the method for rotating coating technique or soaking into naturally on cathode plate, to form and comprise Al
2O
3The silicon oxide film of particle;
(2) ferrocene of 1-10g is dissolved in the 200-400ml acetonitrile obtains ferrocene/acetonitrile solution;
(3) cathode plate that step (1) is made is in 750 ℃ of argon gas roasting 30-45 minute; Be warming up to 930 ℃-950 ℃ by 25 ℃/min, this moment at the heating furnace inlet end with syringe to the cathode plate ferrocene/acetonitrile solution of injecting step (2) preparation off and on;
(4) the cathode plate natural cooling that step (3) is made gets final product.
5. the preparation method of field-transmitting cathode as claimed in claim 4, it is characterized in that, the time of staying of volume, the time interval between every double injection or per injection solution by changing injection solution in the described step (3) is with the size interval parameter of the length, distribution density and the CNT (carbon nano-tube) inner stuffing that change CNT (carbon nano-tube).
6. the preparation method of field-transmitting cathode as claimed in claim 4 is characterized in that, described cathode plate is a conductive silicon chip.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100095101A CN100413010C (en) | 2004-09-03 | 2004-09-03 | Nano carbon tube based field emitting cathode and its preparing method |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100095101A CN100413010C (en) | 2004-09-03 | 2004-09-03 | Nano carbon tube based field emitting cathode and its preparing method |
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| CN1744254A CN1744254A (en) | 2006-03-08 |
| CN100413010C true CN100413010C (en) | 2008-08-20 |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11139815A (en) * | 1997-11-07 | 1999-05-25 | Canon Inc | Carbon nanotube device and its manufacture |
| CN1401562A (en) * | 2002-10-14 | 2003-03-12 | 北京大学 | Carbon nano-tube/ferromagnetism metal nanowire composite material, mfg. method and use thereof |
| JP2003073109A (en) * | 2001-06-20 | 2003-03-12 | Osaka Gas Co Ltd | Carbonous complex material involving cobalt compound and its producing method |
| CN1460639A (en) * | 2003-05-23 | 2003-12-10 | 北京大学 | Carbon base nano tube, its preparation method and application |
-
2004
- 2004-09-03 CN CNB2004100095101A patent/CN100413010C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11139815A (en) * | 1997-11-07 | 1999-05-25 | Canon Inc | Carbon nanotube device and its manufacture |
| JP2003073109A (en) * | 2001-06-20 | 2003-03-12 | Osaka Gas Co Ltd | Carbonous complex material involving cobalt compound and its producing method |
| CN1401562A (en) * | 2002-10-14 | 2003-03-12 | 北京大学 | Carbon nano-tube/ferromagnetism metal nanowire composite material, mfg. method and use thereof |
| CN1460639A (en) * | 2003-05-23 | 2003-12-10 | 北京大学 | Carbon base nano tube, its preparation method and application |
Non-Patent Citations (4)
| Title |
|---|
| 丝网印刷制备碳纳米管场发射阴极的研究. 周雪东，雷威，张宇宁，王琦龙，李俊涛，李家会.真空科学与技术学报，第24卷第1期. 2004 |
| 丝网印刷制备碳纳米管场发射阴极的研究. 周雪东，雷威，张宇宁，王琦龙，李俊涛，李家会.真空科学与技术学报，第24卷第1期. 2004 * |
| 涂布法制备碳纳米管场发射阴极及其性能的研究. 冯涛，李琼，柳襄怀，王曦，徐静芳，诸玉坤.发光学报，第23卷第4期. 2002 |
| 涂布法制备碳纳米管场发射阴极及其性能的研究. 冯涛，李琼，柳襄怀，王曦，徐静芳，诸玉坤.发光学报，第23卷第4期. 2002 * |
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