TWI426540B - Electron emitter and electron emitting element - Google Patents
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本發明涉及一種電子發射體及電子發射元件，尤其涉及一種基於奈米碳管之電子發射體及電子發射元件。 The present invention relates to an electron emitter and an electron emitting element, and more particularly to an electron emitter and an electron emitting element based on a carbon nanotube.
奈米碳管(Carbon Nanotube,CNT)係一種新型碳材料，由日本研究人員Iijima在1991年發現，請參見"Helical Microtubules of Graphitic Carbon",S.Iijima,Nature,vol.354,p56(1991)。奈米碳管具有極優異之導電性能、良好之化學穩定性及大的長徑比，且其具有幾乎接近理論極限之尖端表面積(尖端表面積愈小，其局部電場愈集中)，因而奈米碳管在場發射真空電子源領域具有潛在的應用前景。目前研究表明，奈米碳管係已知的最好的場發射材料之一，它的尖端尺寸只有幾奈米至幾十奈米，具有較低的開啟電壓，可傳輸極大的電流密度，並且電流穩定，使用壽命長，因而非常適合作為一種極佳的點電子源，應用在掃描電子顯微鏡(Scanning Electron Microscope)、透射電子顯微鏡(Transmission Electron Microscope)等設備做為電子發射體。 Carbon Nanotube (CNT) is a new type of carbon material discovered by Japanese researcher Iijima in 1991. See "Helical Microtubules of Graphitic Carbon", S. Iijima, Nature, vol. 354, p56 (1991) . The carbon nanotubes have excellent electrical conductivity, good chemical stability and large aspect ratio, and have a tip surface area close to the theoretical limit (the smaller the tip surface area, the more concentrated the local electric field), thus the nanocarbon The field of field emission vacuum electron source has potential application prospects. Current research shows that the carbon nanotube system is one of the best field emission materials known, its tip size is only a few nanometers to tens of nanometers, has a low turn-on voltage, can transmit a very large current density, and The current is stable and the service life is long, so it is very suitable as an excellent point electron source. It is used as an electron emitter in a scanning electron microscope (Scanning Electron Microscope) or a transmission electron microscope (Transmission Electron Microscope).
現有的電子發射體為一奈米碳管長線。該奈米碳管長線具有一第一端及與第一端相對之第二端。在應用中，該奈米碳管長線之第一端與一導電基體電連接，該奈米碳管長線之第二端從導電基體 向外延伸。所述奈米碳管長線之第二端用做電子發射端。然而，所述奈米碳管長線的製備方法為將一較長的奈米碳管線機械切割後獲得。因此，採用該種奈米碳管長線作為電子發射體時，該電子發射體之電子發射端為平齊結構，所以其電子發射能力較差。 The existing electron emitter is a long carbon nanotube tube. The carbon nanotube long wire has a first end and a second end opposite the first end. In the application, the first end of the long line of the carbon nanotube is electrically connected to a conductive substrate, and the second end of the long line of the carbon nanotube is from the conductive substrate Extend outward. The second end of the long carbon nanotube line is used as an electron emission end. However, the preparation method of the nano carbon tube long line is obtained by mechanically cutting a long nano carbon line. Therefore, when the long carbon wire of the carbon nanotube is used as the electron emitter, the electron emission end of the electron emitter has a flush structure, so that its electron emission capability is poor.
有鑒於此，提供一種具有較佳電子發射能力之電子發射體及採用該電子發射體之電子發射元件實為必要。 In view of the above, it is necessary to provide an electron emitter having a preferable electron emission capability and an electron emission element using the electron emitter.
一種電子發射體，所述電子發射體為複數奈米碳管組成的一奈米碳管管狀結構，所述奈米碳管管狀結構沿所述線狀軸心之一端延伸出複數電子發射尖端，所述電子發射尖端具有一開口，所述奈米碳管管狀結構從開口處延伸出複數奈米碳管束作為複數電子發射尖端。 An electron emitter, wherein the electron emitter is a carbon nanotube tubular structure composed of a plurality of carbon nanotubes, and the tubular structure of the carbon nanotube extends a plurality of electron emission tips along one end of the linear axis. The electron emission tip has an opening, and the carbon nanotube tubular structure extends from the opening a plurality of carbon nanotube bundles as a plurality of electron emission tips.
一種電子發射元件，包括：一導電基體；及一電子發射體，所述電子發射體與所述導電基體電連接，所述電子發射體為複數奈米碳管組成的一奈米碳管管狀結構，所述奈米碳管管狀結構沿所述線狀軸心之一端延伸出複數電子發射尖端，所述電子發射尖端具有一開口，所述奈米碳管管狀結構從開口處延伸出複數奈米碳管束作為複數電子發射尖端。 An electron emitting element comprising: a conductive substrate; and an electron emitter electrically connected to the conductive substrate, wherein the electron emitter is a carbon nanotube tubular structure composed of a plurality of carbon nanotubes The tubular structure of the carbon nanotube extends along one end of the linear axis to form a plurality of electron emission tips, the electron emission tip has an opening, and the tubular structure of the carbon nanotube extends from the opening to a plurality of nanometers The carbon tube bundle acts as a complex electron emission tip.
與先前技術相比，本發明提供的電子發射體及電子發射元件具有以下優點：其一，由於電子發射體包括複數電子發射尖端，因此電子發射體具有較大的發射電流；其二，所述奈米碳管管狀結構之一端延伸出複數電子發射尖端，因此，可有效降低該電子發射體之電場屏蔽效應；其三，所述複數電子發射尖端的尖端狀可增強電子發射體之場增強因子，使電子發射體更易於發射電子，從 而提高電子發射體之場發射性能。 Compared with the prior art, the electron emitter and the electron emitting element provided by the present invention have the following advantages: First, since the electron emitter includes a plurality of electron emission tips, the electron emitter has a large emission current; One end of the tubular structure of the carbon nanotube extends out of the complex electron emission tip, thereby effectively reducing the electric field shielding effect of the electron emitter; thirdly, the tip of the complex electron emission tip enhances the field enhancement factor of the electron emitter To make it easier for electron emitters to emit electrons, from The field emission performance of the electron emitter is improved.
10、20、32‧‧‧電子發射體 10, 20, 32‧‧‧ electron emitters
30‧‧‧電子發射元件 30‧‧‧Electronic emission components
34‧‧‧導電基體 34‧‧‧Electrical substrate
102‧‧‧奈米碳管管狀結構的第一端 102‧‧‧ First end of the tubular structure of the carbon nanotube
104‧‧‧奈米碳管管狀結構的第二端 104‧‧‧The second end of the carbon nanotube tubular structure
106、206、306‧‧‧電子發射尖端 106, 206, 306‧‧‧ Electron emission tip
108‧‧‧電子發射部 108‧‧‧Electronic Launch Department
110‧‧‧開口 110‧‧‧ openings
210‧‧‧奈米碳管層 210‧‧‧Nano carbon tube layer
212‧‧‧電子發射部 212‧‧‧Electronic Launch Department
220‧‧‧導電線狀結構 220‧‧‧Electrical wire structure
圖1係本發明第一實施例提供之電子發射體的結構示意圖。 1 is a schematic structural view of an electron emitter provided by a first embodiment of the present invention.
圖2係本發明第一實施例提供之電子發射體的掃描電鏡照片。 2 is a scanning electron micrograph of an electron emitter provided by a first embodiment of the present invention.
圖3係本發明第一實施例提供之電子發射體的剖視圖。 Figure 3 is a cross-sectional view showing an electron emitter provided by a first embodiment of the present invention.
圖4係本發明第一實施例提供之電子發射體的電子發射部的掃描電鏡照片。 4 is a scanning electron micrograph of an electron-emitting portion of an electron emitter provided by a first embodiment of the present invention.
圖5係本發明第一實施例提供之電子發射體的開口的掃描電鏡照片。 Figure 5 is a scanning electron micrograph of an opening of an electron emitter provided by a first embodiment of the present invention.
圖6係本發明第一實施例提供的電子發射體的電子發射尖端的透射電鏡照片。 Fig. 6 is a transmission electron micrograph of an electron-emitting tip of an electron emitter provided by a first embodiment of the present invention.
圖7係本發明第一實施例提供之奈米碳管預製體的掃描電鏡照片。 Figure 7 is a scanning electron micrograph of a carbon nanotube preform provided in a first embodiment of the present invention.
圖8係本發明第二實施例提供之電子發射體的剖視圖。 Figure 8 is a cross-sectional view showing an electron emitter provided by a second embodiment of the present invention.
圖9係採用上述實施例電子發射體的電子發射元件的結構示意圖。 Fig. 9 is a view showing the structure of an electron-emitting device using the electron emitter of the above embodiment.
以下將結合附圖詳細說明本發明實施例的電子發射體及電子發射元件。 Hereinafter, an electron emitter and an electron emitting element of an embodiment of the present invention will be described in detail with reference to the accompanying drawings.
請參閱圖1、圖2、圖3及圖4，本發明第一實施例提供一種電子發射體10。所述電子發射體10為一奈米碳管管狀結構，所述奈米碳管管狀結構具有一中空之線狀軸心，所述奈米碳管管狀結構為複 數奈米碳管圍繞該中空之線狀軸心組成，所述奈米碳管管狀結構沿線狀軸心的一端延伸出複數電子發射尖端106。所述奈米碳管管狀結構中複數奈米碳管通過凡得瓦力相互連接成一體結構。所述奈米碳管管狀結構中大多數奈米碳管通過凡得瓦力首尾相連並圍繞中空之線狀軸心螺旋延伸。可以理解，該奈米碳管管狀結構中也存在少數隨機排列的奈米碳管。該少數隨機排列的奈米碳管之延伸方向沒有規則。然，所述少數隨機排列的奈米碳管不影響所述奈米碳管管狀結構中大多數奈米碳管的排列方式與延伸方向。在此，將線狀軸心的長度方向定義為複數奈米碳管的延伸方向，將複數奈米碳管圍繞所述線狀軸心螺旋形成的方向定義為螺旋方向。在螺旋方向上相鄰的奈米碳管通過凡得瓦力首尾相連，在延伸方向上相鄰的奈米碳管通過凡得瓦力緊密結合。該奈米碳管管狀結構中的大多數奈米碳管的螺旋方向與所述線狀軸心之長度方向形成一定的交叉角α，且α大於0°且小於等於90°。 Referring to FIG. 1 , FIG. 2 , FIG. 3 and FIG. 4 , a first embodiment of the present invention provides an electron emitter 10 . The electron emitter 10 is a tubular structure of a carbon nanotube having a hollow linear axis, and the tubular structure of the carbon nanotube is a complex A plurality of carbon nanotubes are formed around the hollow linear axis, and the carbon nanotube tubular structure extends from the one end of the linear axis to the plurality of electron emitting tips 106. The plurality of carbon nanotubes in the tubular structure of the carbon nanotubes are connected to each other by a van der Waals force to form an integral structure. Most of the carbon nanotubes in the tubular structure of the carbon nanotubes are connected end to end by a van der Waals force and spirally extend around the hollow axis of the hollow. It can be understood that there are also a small number of randomly arranged carbon nanotubes in the tubular structure of the carbon nanotube. There is no rule in the direction in which the few randomly arranged carbon nanotubes extend. However, the few randomly arranged carbon nanotubes do not affect the arrangement and extension direction of most of the carbon nanotubes in the tubular structure of the carbon nanotubes. Here, the longitudinal direction of the linear axis is defined as the extending direction of the plurality of carbon nanotubes, and the direction in which the plurality of carbon nanotubes are spirally formed around the linear axis is defined as the spiral direction. The carbon nanotubes adjacent in the spiral direction are connected end to end by the van der Waals force, and the adjacent carbon nanotubes in the extending direction are tightly coupled by the van der Waals force. The helical direction of most of the carbon nanotubes in the tubular structure of the carbon nanotube forms a certain crossing angle α with the longitudinal direction of the linear axis, and α is greater than 0° and less than or equal to 90°.
所述線狀軸心係空的，係虛擬的，係該奈米碳管管狀結構之軸心。該線狀軸心之截面形狀可為方形、梯形、圓形或橢圓形等形狀，該線狀軸心之截面大小，可根據實際要求而定。 The linear axis is hollow and is virtual, and is the axis of the tubular structure of the carbon nanotube. The cross-sectional shape of the linear axis may be square, trapezoidal, circular or elliptical, and the cross-sectional size of the linear axis may be determined according to actual requirements.
所述奈米碳管管狀結構之一端具有複數電子發射尖端106，所述複數電子發射尖端106圍繞所述線狀軸心呈環形排列。具體地，所述奈米碳管管狀結構在沿線狀軸心長度之方向具有一第一端102及與該第一端102相對的一第二端104。在第二端104，所述奈米碳管管狀結構的整體直徑沿遠離第一端102之方向逐漸減小，並收縮形成一類圓錐形的縮口，作為所述電子發射體10的電子發射部108。所述電子發射體10在應用時，在電場作用下從電子發 射部108發射出電子，由於電子發射體10的電子發射部108為類圓錐形，可使電子發射部108的局部電場集中，因此可增強電子發射部108的場增強因子，使電子發射體10易於發射出電子。 One end of the tubular structure of the carbon nanotube has a plurality of electron emission tips 106, and the plurality of electron emission tips 106 are arranged in a ring shape around the linear axis. Specifically, the carbon nanotube tubular structure has a first end 102 and a second end 104 opposite the first end 102 in the direction of the length of the linear axis. At the second end 104, the overall diameter of the tubular structure of the carbon nanotubes gradually decreases in a direction away from the first end 102, and contracts to form a conical shaped constriction as an electron emission portion of the electron emitter 10. 108. When the electron emitter 10 is applied, it is emitted from the electron under the action of an electric field. The emitter 108 emits electrons, and since the electron-emitting portion 108 of the electron emitter 10 is conical, the local electric field of the electron-emitting portion 108 can be concentrated, so that the field enhancement factor of the electron-emitting portion 108 can be enhanced, and the electron-emitting body 10 can be made. Easy to emit electrons.
請一併參閱圖5，所述類圓錐形的電子發射部108的末端具有一開口110，及複數突出的奈米碳管束。即，所述奈米碳管管狀結構具有複數電子發射尖端106的一端具有一開口110，所述奈米碳管管狀結構從開口110處延伸出複數奈米碳管束作為複數電子發射尖端106。該複數奈米碳管束為所述奈米碳管管狀結構從第二端104延伸出來的複數由奈米碳管組成的束狀結構。該複數奈米碳管束圍繞所述線狀軸心呈環狀排列，作為複數電子發射尖端106。由於該複數電子發射尖端106呈環形排列，因此，該複數電子發射尖端106之間的間距較大，降低了該複數電子發射尖端106之間的電場屏蔽效應。該複數奈米碳管束之延伸方向基本一致，即該複數電子發射尖端106基本沿所述線狀軸心之長度方向向遠離奈米碳管管狀結構的方向延伸，所述遠離奈米碳管管狀結構之方向係指遠離奈米碳管管狀結構之第一端102的方向延伸。進一步的，該複數奈米碳管束圍繞所述線狀軸心呈發散狀排列，即該複數電子發射尖端106之延伸方向逐漸遠離所述線狀軸心。當該複數奈米碳管束呈發散狀排列時，雖然所述電子發射部108之徑向尺寸為沿遠離奈米碳管管狀結構之第一端102方向逐漸減小，但複數電子發射尖端106呈發散性的排列，進而電子發射部108的末端向外略微擴張，從而複數電子發射尖端106之間的距離沿延伸方向逐漸變大，使開口110處的複數電子發射尖端106相互間的間距更加擴大，降低了電子發射尖端106之間的電場屏蔽效應。所述開口110的徑向尺寸範圍為4微米-6微米，本實施例中，所述開 口110為圓形，所述開口110的徑向尺寸為5微米，因此位於開口110的相對二端的電子發射尖端106的間距大於等於5微米。 Referring to FIG. 5 together, the end of the conical electron-emitting portion 108 has an opening 110 and a plurality of protruding carbon nanotube bundles. That is, the carbon nanotube tubular structure having a plurality of electron-emitting tips 106 has an opening 110 at one end thereof, and the carbon nanotube tubular structure extends from the opening 110 as a plurality of carbon nanotube bundles as the plurality of electron-emitting tips 106. The plurality of carbon nanotube bundles are bundle structures of a plurality of carbon nanotube tubes extending from the second end 104 of the tubular structure of the carbon nanotubes. The plurality of carbon nanotube bundles are arranged in a ring shape around the linear axis as a plurality of electron emission tips 106. Since the plurality of electron-emitting tips 106 are arranged in a ring shape, the spacing between the plurality of electron-emitting tips 106 is large, reducing the electric field shielding effect between the plurality of electron-emitting tips 106. The plurality of carbon nanotube bundles extend substantially in the same direction, that is, the plurality of electron emission tips 106 extend substantially along the length direction of the linear axis toward the tubular structure of the carbon nanotubes. The direction of the structure means extending away from the first end 102 of the tubular structure of the carbon nanotube. Further, the plurality of carbon nanotube bundles are arranged in a divergent manner around the linear axis, that is, the extension direction of the plurality of electron emission tips 106 gradually moves away from the linear axis. When the plurality of carbon nanotube bundles are arranged in a divergent manner, although the radial dimension of the electron-emitting portion 108 is gradually decreased in a direction away from the first end 102 of the tubular structure of the carbon nanotube, the plurality of electron-emitting tips 106 are The divergent arrangement, and the end of the electron-emitting portion 108 is slightly expanded outward, so that the distance between the plurality of electron-emitting tips 106 gradually increases in the extending direction, so that the distance between the plurality of electron-emitting tips 106 at the opening 110 is further enlarged. The electric field shielding effect between the electron emission tips 106 is reduced. The radial dimension of the opening 110 ranges from 4 micrometers to 6 micrometers. In this embodiment, the opening The port 110 is circular, and the opening 110 has a radial dimension of 5 μm, so that the distance between the electron-emitting tips 106 at opposite ends of the opening 110 is greater than or equal to 5 μm.
請一併參閱圖6，每一電子發射尖端106包括複數基本平行排列的奈米碳管，並且每一電子發射尖端106的頂端突出有一根奈米碳管，即所述複數平行排列的奈米碳管的中心位置突出一根奈米碳管。該突出的奈米碳管的底端(即突出的奈米碳管的非自由端)周圍還圍繞有複數奈米碳管，該複數圍繞的奈米碳管起到固定該突出的奈米碳管的作用。該突出奈米碳管的直徑小於5奈米。本實施例中突出的奈米碳管的直徑為4奈米。由於該突出的奈米碳管之直徑極其小，因此，該突出之奈米碳管具有十分大的長徑比，進而增加了該突出之奈米碳管之場增強因子，使該突出之奈米碳管之場發射性能優異。所述複數電子發射尖端106中相鄰的電子發射尖端106中的突出之奈米碳管之間的距離為0.1微米至2微米。相鄰的二電子發射尖端106中的突出的奈米碳管之間的距離與突出的奈米碳管直徑的比例的範圍為20：1至500：1。可以理解，相鄰的電子發射尖端106的突出的奈米碳管之間的間距遠大於突出的奈米碳管的直徑，可有效降低相鄰的突出奈米碳管之間的電場屏蔽效應。 Referring to FIG. 6 together, each electron emission tip 106 includes a plurality of substantially parallel arranged carbon nanotubes, and a tip of each electron emission tip 106 protrudes from a carbon nanotube, that is, the plurality of parallel arranged nanometers. A carbon nanotube protrudes from the center of the carbon tube. The bottom end of the protruding carbon nanotube (ie, the non-free end of the protruding carbon nanotube) is also surrounded by a plurality of carbon nanotubes, and the plurality of surrounding carbon nanotubes serve to fix the protruding nanocarbon The role of the tube. The protruding carbon nanotubes have a diameter of less than 5 nanometers. The protruding carbon nanotubes in this embodiment have a diameter of 4 nm. Since the diameter of the protruding carbon nanotube is extremely small, the protruding carbon nanotube has a very large aspect ratio, thereby increasing the field enhancement factor of the protruding carbon nanotube, so that the protruding Nana The carbon nanotubes have excellent field emission performance. The distance between the protruding carbon nanotubes in adjacent electron-emitting tips 106 of the plurality of electron-emitting tips 106 is between 0.1 micrometers and 2 micrometers. The ratio of the distance between the protruding carbon nanotubes in the adjacent two electron emission tips 106 to the diameter of the protruding carbon nanotubes ranges from 20:1 to 500:1. It can be understood that the spacing between the protruding carbon nanotubes of the adjacent electron-emitting tips 106 is much larger than the diameter of the protruding carbon nanotubes, which can effectively reduce the electric field shielding effect between adjacent protruding carbon nanotubes.
具體的，所述奈米碳管管狀結構係由至少一奈米碳管膜或至少一奈米碳管線沿該線狀軸心的軸向緊密環繞而形成。可以理解，該奈米碳管管狀結構的管壁具有一定的厚度，所述厚度可以通過控制所環繞奈米碳管膜或奈米碳管線之層數確定。該奈米碳管管狀結構內徑及外徑的大小可以根據實際需求製備。優選地，該奈米碳管管狀結構的內徑範圍為2微米至100微米，外徑為10微米至 120微米。優選地，該奈米碳管管狀結構的內徑範圍為10微米至40微米，外徑為20微米至50微米。本實施例中，該奈米碳管管狀結構的內徑約為18微米，外徑約為30微米。 Specifically, the tubular structure of the carbon nanotubes is formed by tightly surrounding at least one carbon nanotube film or at least one nano carbon line along the axial direction of the linear axis. It will be appreciated that the tube wall of the tubular structure of the carbon nanotubes has a thickness which can be determined by controlling the number of layers surrounding the carbon nanotube membrane or the carbon nanotube line. The inner diameter and the outer diameter of the tubular structure of the carbon nanotube can be prepared according to actual needs. Preferably, the carbon nanotube tubular structure has an inner diameter ranging from 2 micrometers to 100 micrometers and an outer diameter of 10 micrometers to 120 microns. Preferably, the carbon nanotube tubular structure has an inner diameter ranging from 10 micrometers to 40 micrometers and an outer diameter of 20 micrometers to 50 micrometers. In this embodiment, the tubular structure of the carbon nanotube has an inner diameter of about 18 microns and an outer diameter of about 30 microns.
本發明提供之電子發射體10可在電場作用下發射出電子，故，該電子發射體10可以應用於場發射領域之場發射器件中、掃描電子顯微鏡及透射電子顯微鏡。該場發射器件具有至少一第一導電體及一第二導電體。該電子發射體10之第一端102可與場發射器件中的第一導電體電連接，電子發射體10之第二端104指向第二導電體。所述第一導電體及第二導電體共同作用從而施加一電場於該電子發射體10。該電子發射體10在電場之作用下發射出電子。 The electron emitter 10 provided by the present invention can emit electrons under the action of an electric field. Therefore, the electron emitter 10 can be applied to field emission devices in the field of field emission, scanning electron microscope and transmission electron microscope. The field emission device has at least a first electrical conductor and a second electrical conductor. The first end 102 of the electron emitter 10 can be electrically coupled to a first electrical conductor in the field emission device, and the second end 104 of the electron emitter 10 is directed to the second electrical conductor. The first electrical conductor and the second electrical conductor cooperate to apply an electric field to the electron emitter 10. The electron emitter 10 emits electrons under the action of an electric field.
所述電子發射體10的製備方法，包括以下步驟：(S10)提供一線狀支撐體；(S20)提供至少一奈米碳管膜或至少一奈米碳管線，將所述至少一奈米碳管膜或至少一奈米碳管線纏繞在所述線狀支撐體表面形成一奈米碳管層；(S30)移除所述線狀支撐體，得到一由奈米碳管層圍成的管狀奈米碳管預製體；及(S40)將該管狀奈米碳管預製體熔斷，形成所述電子發射體10。 The method for preparing the electron emitter 10 includes the following steps: (S10) providing a linear support; (S20) providing at least one carbon nanotube film or at least one nano carbon line, the at least one nanocarbon a tubular film or at least one nano carbon line is wound around the surface of the linear support to form a carbon nanotube layer; (S30) removing the linear support to obtain a tubular naphthalene surrounded by a carbon nanotube layer a carbon nanotube preform; and (S40) blowing the tubular carbon nanotube preform to form the electron emitter 10.
在步驟(S10)中，該線狀支撐體在一控制裝置的控制下既能夠繞其中心軸旋轉又能夠沿其中心軸延伸方向做直線運動。 In the step (S10), the linear support body is both rotatable about its central axis and linearly movable along the direction of its central axis under the control of the control device.
所述線狀支撐體之材料可為單質金屬、金屬合金或高分子材料等。所述單質金屬包括金、銀、銅或鋁等，所述金屬合金包括銅錫合金等。進一步的，所述銅錫合金表面可鍍銀。所述銅錫合金可為97%銅與3%錫的合金。 The material of the linear support may be an elemental metal, a metal alloy or a polymer material. The elemental metal includes gold, silver, copper or aluminum, etc., and the metal alloy includes a copper-tin alloy or the like. Further, the surface of the copper-tin alloy may be plated with silver. The copper-tin alloy may be an alloy of 97% copper and 3% tin.
所述線狀支撐體在纏繞奈米碳管膜或奈米碳管線的過程中，主要 起支撐作用，其本身具有一定的穩定性及機械強度，且可通過化學方法、物理方法或機械方法移除。因此，該線狀支撐體之材料可選用符合上述條件的所有材料，不限於上述列舉的幾種。可以理解，該線狀支撐體可以選用不同的直徑。本實施例中選用直徑為18微米的金線作為該線狀支撐體。 The linear support body is mainly wound in the process of winding a carbon nanotube film or a carbon carbon line. Supporting, it has certain stability and mechanical strength, and can be removed by chemical, physical or mechanical methods. Therefore, the material of the linear support may be selected from all materials satisfying the above conditions, and is not limited to the above-listed ones. It can be understood that the linear support body can be selected from different diameters. In this embodiment, a gold wire having a diameter of 18 μm is selected as the linear support.
在步驟(S20)中所述至少一奈米碳管膜或至少一奈米碳管線為自支撐結構。具體地，所述奈米碳管膜可為奈米碳管拉膜、奈米碳管絮化膜或奈米碳管碾壓膜等。所述奈米碳管膜由若干奈米碳管組成，該若干奈米碳管無序或有序排列。所謂無序排列係指奈米碳管的排列方向無規則。所謂有序排列係指奈米碳管的排列方向有規則。具體地，當奈米碳管膜包括無序排列的奈米碳管時，奈米碳管相互纏繞或者各向同性排列；當奈米碳管膜包括有序排列的奈米碳管時，奈米碳管沿一方向或者複數方向擇優取向延伸。所謂“擇優取向”係指所述奈米碳管膜中的大多數奈米碳管在一方向或幾個方向上具有較大的取向幾率；即，該奈米碳管膜中的大多數奈米碳管的軸向基本沿同一方向或幾個方向延伸。 In the step (S20), the at least one carbon nanotube film or the at least one nano carbon line is a self-supporting structure. Specifically, the carbon nanotube film may be a carbon nanotube film, a carbon nanotube film or a carbon nanotube film. The carbon nanotube membrane is composed of a plurality of carbon nanotubes, which are disorderly or orderedly arranged. The so-called disordered arrangement means that the arrangement direction of the carbon nanotubes is irregular. The so-called ordered arrangement means that the arrangement direction of the carbon nanotubes is regular. Specifically, when the carbon nanotube film comprises a disordered arrangement of carbon nanotubes, the carbon nanotubes are entangled or isotropically arranged; when the carbon nanotube film comprises an ordered arrangement of carbon nanotubes, The carbon nanotubes extend in a preferred orientation in one direction or in a plurality of directions. By "preferable orientation" is meant that most of the carbon nanotubes in the carbon nanotube membrane have a greater probability of orientation in one or more directions; that is, most of the naphthalene membranes. The axial direction of the carbon nanotubes extends substantially in the same direction or in several directions.
當所述奈米碳管膜為奈米碳管拉膜或奈米碳管線時，步驟(S20)可具體包括以下步驟：步驟(S210)，形成至少一奈米碳管陣列。 When the carbon nanotube film is a carbon nanotube film or a nano carbon line, the step (S20) may specifically include the following steps: step (S210), forming at least one carbon nanotube array.
提供一基底，所述奈米碳管陣列形成於所述基底表面。所述奈米碳管陣列由複數奈米碳管組成，該奈米碳管為單壁奈米碳管、雙壁奈米碳管及多壁奈米碳管中的一種或數種。本實施例中，該複數奈米碳管為多壁奈米碳管，且該複數奈米碳管基本上相互平行且垂直於所述基底，該奈米碳管陣列不含雜質，如無定型碳或殘 留的催化劑金屬顆粒等。所述奈米碳管陣列的製備方法包括化學氣相沈積法、電弧放電法、鐳射燒蝕法等，所述奈米碳管陣列之製備方法不限。優選地，該奈米碳管陣列為超順排奈米碳管陣列。 A substrate is provided, the array of carbon nanotubes being formed on a surface of the substrate. The carbon nanotube array is composed of a plurality of carbon nanotubes, one or several of a single-walled carbon nanotube, a double-walled carbon nanotube, and a multi-walled carbon nanotube. In this embodiment, the plurality of carbon nanotubes are multi-walled carbon nanotubes, and the plurality of carbon nanotubes are substantially parallel to each other and perpendicular to the substrate, and the array of carbon nanotubes contains no impurities, such as amorphous Carbon or residual Residual catalyst metal particles, etc. The preparation method of the carbon nanotube array includes a chemical vapor deposition method, an arc discharge method, a laser ablation method, and the like, and the preparation method of the carbon nanotube array is not limited. Preferably, the array of carbon nanotubes is a super-sequential carbon nanotube array.
步驟(S220)，從所述奈米碳管陣列中拉取獲得一奈米碳管拉膜或奈米碳管線。 In step (S220), a carbon nanotube film or a nanocarbon line is obtained by drawing from the carbon nanotube array.
本實施例採用具有一定寬度之膠帶、鑷子或夾子接觸奈米碳管陣列以選定一具有一定寬度之複數奈米碳管；以一定速度拉伸該選定之奈米碳管，該拉取方向沿基本垂直於奈米碳管陣列的生長方向。從而使得奈米碳管首尾相連地被拉出，進而形成一連續的奈米碳管拉膜。在上述拉伸過程中，該複數奈米碳管片段在拉力作用下沿拉伸方向逐漸脫離基底的同時，由於凡得瓦力作用，在拉伸方向上相鄰的複數奈米碳管之間首尾相連地連續地被拉出，從而形成一連續、均勻且具有一定寬度的奈米碳管拉膜。該奈米碳管拉膜的寬度與奈米碳管陣列所生長的基底的尺寸有關，該奈米碳管拉膜的長度不限，可根據實際需求制得。所述奈米碳管拉膜的結構及其製備方法請參見范守善等人於2007年2月12日申請的，於2010年07月11日公告的第I327177號之中華民國專利說明書。可以理解，當該奈米碳管拉膜的寬度很窄的情況下，可以形成所述奈米碳管線。 In this embodiment, a carbon nanotube array having a certain width is used to contact the carbon nanotube array to select a plurality of carbon nanotubes having a certain width; and the selected carbon nanotubes are stretched at a certain speed, the pulling direction along the pulling direction It is substantially perpendicular to the growth direction of the nanotube array. Thereby, the carbon nanotubes are pulled out end to end, thereby forming a continuous carbon nanotube film. In the above stretching process, the plurality of carbon nanotube segments are gradually separated from the substrate in the stretching direction under the action of the tensile force, and the plurality of carbon nanotubes adjacent to each other in the stretching direction are affected by the van der Waals force. The film is continuously pulled out end to end to form a continuous, uniform, and wide-width carbon nanotube film. The width of the carbon nanotube film is related to the size of the substrate on which the carbon nanotube array is grown. The length of the carbon nanotube film is not limited and can be obtained according to actual needs. For the structure of the carbon nanotube film and the preparation method thereof, please refer to the Republic of China patent specification No. I327177 which was filed on February 11, 2010 by Fan Shoushan et al. It can be understood that the nanocarbon line can be formed when the width of the carbon nanotube film is narrow.
步驟(S230)，將所述至少一奈米碳管拉膜或至少一奈米碳管線纏繞於所述線狀支撐體上形成一奈米碳管層。 In step (S230), the at least one carbon nanotube film or at least one nano carbon line is wound on the linear support to form a carbon nanotube layer.
將所述奈米碳管拉膜或奈米碳管線纏繞於所述線狀支撐體上形成一奈米碳管層的方法包括以下步驟：首先，將通過以上方法製備 的所述奈米碳管拉膜或奈米碳管線的一端固定於所述線狀支撐體表面；其次，使該線狀支撐體繞其中心軸旋轉的同時沿其中心軸延伸方向做直線運動，即可得到一表面螺旋纏繞有奈米碳管拉膜或奈米碳管線的線狀支撐體。其中，所述奈米碳管拉膜或奈米碳管線中大多數奈米碳管的螺旋方向與線狀支撐體的軸心的延伸方向具有一定的交叉角α，α大於0°且小於等於90°。可以理解，在奈米碳管拉膜厚度或奈米碳管線直徑一定的情況下，交叉角α越小，則纏繞得到的奈米碳管層就越薄，交叉角α越大，則纏繞得到的奈米碳管層的厚度就越厚。本實施例中，將一奈米碳管拉膜纏繞於一直徑為18微米的金線的表面。所述奈米碳管拉膜的纏繞厚度為6微米，通過將一奈米碳管拉膜的一端固定於所述金線的表面，使金線繞其中心軸旋轉同時沿其中心軸延伸方向做直線運動，從而使奈米碳管拉膜纏繞於金線的表面。 The method of winding the carbon nanotube film or nano carbon line on the linear support to form a carbon nanotube layer comprises the following steps: First, the method is prepared by the above method One end of the carbon nanotube film or nano carbon line is fixed to the surface of the linear support; secondly, the linear support is linearly moved along the central axis while rotating about its central axis A linear support having a surface spirally wound with a carbon nanotube film or a nanocarbon line can be obtained. Wherein, the spiral direction of most of the carbon nanotubes in the carbon nanotube film or the nanocarbon pipeline has a certain intersection angle α with the extending direction of the axis of the linear support body, and α is greater than 0° and less than or equal to 90°. It can be understood that, in the case where the thickness of the carbon nanotube film or the diameter of the carbon nanotube line is constant, the smaller the cross angle α, the thinner the carbon nanotube layer obtained by winding, and the larger the crossing angle α, the winding is obtained. The thicker the carbon nanotube layer is. In this embodiment, a carbon nanotube film is wound around a surface of a gold wire having a diameter of 18 μm. The carbon nanotube film is wound to a thickness of 6 micrometers, and a gold wire is rotated around a central axis thereof while extending along a central axis thereof by fixing one end of a carbon nanotube film to the surface of the gold wire. Make a linear motion so that the carbon nanotube film is wound around the surface of the gold wire.
步驟(S30)，移除所述線狀支撐體，得到一由奈米碳管層圍成的管狀的奈米碳管預製體。 Step (S30), removing the linear support body to obtain a tubular carbon nanotube preform surrounded by a carbon nanotube layer.
將所述之線狀支撐體通過化學方法、物理方法或機械方法移除。當採用活潑的單質金屬材料或金屬合金作該線狀支撐體時，如鐵或鋁及其合金，可使用一酸性溶液與該活潑的金屬材料反應，將該線狀支撐體移除，例如採用濃度為0.5mol/L的鹽酸溶液腐蝕鋁線，將鋁線移除。當採用不活潑的單質金屬材料或金屬合金作該線狀支撐體時，如金或銀及其合金，可使用加熱蒸發的方法，移除所述線狀支撐體；當採用高分子材料作線狀支撐體時，可以使用一拉伸裝置沿所述線狀支撐體的中心軸方向拉出所述線狀支撐體。可以理解，根據線狀支撐體直徑的不同可得到不同內徑的管 狀奈米碳管預製體。金線的移除可通過將所述奈米碳管層及金線之二端分別連接一電極，在真空環境中，通過電極給奈米碳管層及金線通電流，使奈米碳管層及金線升溫，當溫度升高到高於金線的熔點時，金線被蒸發從而去除。 The linear support is removed by chemical, physical or mechanical means. When a reactive elemental metal material or metal alloy is used as the linear support, such as iron or aluminum and its alloy, an acidic solution may be reacted with the active metal material to remove the linear support, for example, The aluminum wire was etched by a hydrochloric acid solution having a concentration of 0.5 mol/L, and the aluminum wire was removed. When an inert elemental metal material or metal alloy is used as the linear support, such as gold or silver and its alloy, the linear support can be removed by heating and evaporation; when a polymer material is used as the wire In the case of the support, the linear support may be pulled out along the central axis direction of the linear support using a stretching device. It can be understood that different inner diameter tubes can be obtained according to the diameter of the linear support body. Shaped carbon nanotube preform. The removal of the gold wire can be carried out by connecting the two ends of the carbon nanotube layer and the gold wire to an electrode, and passing the current to the carbon nanotube layer and the gold wire through the electrode in a vacuum environment to make the carbon nanotube The layer and the gold wire are heated, and when the temperature rises above the melting point of the gold wire, the gold wire is evaporated to be removed.
請參閱圖7，本實施例中，該管狀奈米碳管預製體中的大多數奈米碳管均首尾相連地沿着線狀軸心的長度方向螺旋狀延伸。該管狀奈米碳管預製體中的大多數奈米碳管中每一奈米碳管與在延伸方向上相鄰的奈米碳管通過凡得瓦力首尾相連。該大多數奈米碳管中每一奈米碳管的延伸方向與所述管狀奈米碳管預製體的線狀軸心的長度方向形成一定的交叉角α，α大於0°且小於等於90°。 Referring to FIG. 7, in the embodiment, most of the carbon nanotubes in the tubular carbon nanotube preform are spirally extended end to end along the length of the linear axis. Each of the carbon nanotubes in the majority of the nanotubes in the tubular carbon nanotube preform is connected end to end with a vanadium tube in the extending direction. The extending direction of each of the carbon nanotubes in the majority of the carbon nanotubes forms a certain intersection angle α with the longitudinal direction of the linear axis of the tubular carbon nanotube preform, and α is greater than 0° and less than or equal to 90. °.
步驟(S40)，將該管狀奈米碳管預製體熔斷，形成所述電子發射體。 In step (S40), the tubular carbon nanotube preform is melted to form the electron emitter.
該管狀奈米碳管預製體的熔斷方法包括電流熔斷法、電子轟擊法及鐳射照射法。所述管狀奈米碳管預製體在沿其中空線狀軸心的長度方向的一處位置發生熔斷，所述管狀奈米碳管預製體在熔斷處形成複數奈米碳管束，形成二電子發射體10。 The method of fusing the tubular carbon nanotube preform includes a current fusing method, an electron bombardment method, and a laser irradiation method. The tubular carbon nanotube preform is melted at a position along the length direction of the hollow axis, and the tubular carbon nanotube preform forms a plurality of carbon nanotube bundles at the fuse to form a two-electron emission Body 10.
方法一：電流熔斷法，即將該管狀奈米碳管預製體通電流加熱熔斷。方法一可以在真空環境下或惰性氣體保護環境下進行，其具體包括以下步驟：首先，將該管狀奈米碳管預製體懸空設置於一真空室內或充滿惰性氣體之反應室。 Method 1: Current fusing method, that is, the tubular carbon nanotube preform is heated and blown by current. The method 1 can be carried out under a vacuum environment or an inert gas protection environment, and specifically includes the following steps: First, the tubular carbon nanotube preform is suspended in a vacuum chamber or a reaction chamber filled with an inert gas.
該真空室包括一可視視窗及一陽極接線柱與一陰極接線柱，且其 真空度低於1×10-1帕，優選為2×10-5帕。該管狀奈米碳管預製體二端分別與陽極接線柱及陰極接線柱電性連接。本實施例中，該陽極接線柱與陰極接線柱為直徑0.5毫米的銅絲導線。 The vacuum chamber includes a visible window and an anode terminal and a cathode terminal, and has a vacuum of less than 1 × 10 -1 Pa, preferably 2 × 10 -5 Pa. The two ends of the tubular carbon nanotube preform are electrically connected to the anode terminal and the cathode terminal, respectively. In this embodiment, the anode terminal and the cathode terminal are copper wire wires having a diameter of 0.5 mm.
所述充滿惰性氣體的反應室結構與真空室相同，惰性氣體可為氦氣或氬氣等。 The reaction chamber filled with an inert gas has the same structure as the vacuum chamber, and the inert gas may be helium or argon.
其次，在該管狀奈米碳管預製體二端施加一電壓，通入電流加熱熔斷。 Next, a voltage is applied to both ends of the tubular carbon nanotube preform, and a current is applied to heat the fuse.
在陽極接線柱與陰極接線柱之間施加一40伏特的直流電壓。本技術領域人員應當明白，陽極接線柱與陰極接線柱之間施加的電壓與所選的奈米碳管預製體的內徑、外經、壁厚及長度有關。在直流條件下通過焦耳熱加熱管狀奈米碳管預製體。加熱溫度優選為2000K至2400K，加熱時間小於1小時。在真空直流加熱過程中，通過管狀奈米碳管預製體的電流會逐漸上升，但很快電流就開始下降直到管狀奈米碳管預製體被熔斷。在熔斷前，管狀奈米碳管預製體上會出現一亮點，管狀奈米碳管預製體從該亮點處熔斷。 A 40 volt DC voltage is applied between the anode and cathode posts. Those skilled in the art will appreciate that the voltage applied between the anode and cathode posts is related to the inner diameter, outer diameter, wall thickness and length of the selected carbon nanotube preform. The tubular carbon nanotube preform is heated by Joule heat under direct current conditions. The heating temperature is preferably from 2000 K to 2400 K, and the heating time is less than 1 hour. During vacuum DC heating, the current through the tubular carbon nanotube preform gradually rises, but the current begins to drop until the tubular carbon nanotube preform is blown. Before the fusing, a bright spot appears on the tubular carbon nanotube preform, from which the tubular carbon nanotube preform is blown.
由於管狀奈米碳管預製體中各點的電阻不同，使得各點的分電壓也不同。在管狀奈米碳管預製體中電阻較大的一點，會得到較大的分電壓，從而具有較大的加熱功率，產生較多的焦耳熱，使該點的溫度迅速升高。在熔斷的過程中，該點的電阻會越來越大，導致該點的分電壓也越來越大，同時，溫度也越來越大直到該點斷裂，形成二電子發射體。在熔斷的瞬間，陰極與陽極之間會產生一非常小的間隙，同時在熔斷點位置附近，由於碳的蒸發，真空度較差，這些因素會使熔斷的瞬間在熔斷點附近產生氣體電離。電離後的離子轟擊熔斷的管狀奈米碳管預製體的端部，在所述 管狀奈米碳管預製體端部形成複數奈米碳管束，從而在該奈米碳管管狀結構的一端形成複數電子發射尖端106。由於在熔斷的過程中，越靠近熔斷點，碳原子蒸發的越多，從而使管狀奈米碳管預製體的一端形成一縮口。 Since the resistance of each point in the tubular carbon nanotube preform is different, the partial voltages at the respective points are also different. In the tubular carbon nanotube preform, a larger resistance will result in a larger partial voltage, which has a larger heating power, and generates more Joule heat, so that the temperature at this point rises rapidly. During the fusing process, the resistance at this point will become larger and larger, resulting in a larger and higher partial voltage at that point, and at the same time, the temperature is also getting larger until the point breaks, forming a two-electron emitter. At the moment of melting, a very small gap is generated between the cathode and the anode, and at the same time, near the position of the melting point, the degree of vacuum is poor due to evaporation of carbon, and these factors cause gas ionization to occur near the melting point at the moment of melting. Ionized ion bombardment of the end of the blown tubular carbon nanotube preform, A plurality of carbon nanotube bundles are formed at the ends of the tubular carbon nanotube preform to form a plurality of electron-emitting tips 106 at one end of the tubular structure of the carbon nanotubes. The closer the melting point is, the more the carbon atoms evaporate during the fusing process, thereby forming a constriction at one end of the tubular carbon nanotube preform.
本實施例採用的真空熔斷法，避免了奈米碳管預製體熔斷後得到的奈米碳管管狀結構一端的複數電子發射尖端106的污染，而且，加熱過程中奈米碳管預製體的機械強度會有一定提高，使之具備優良的場發射性能。 The vacuum melting method used in the embodiment avoids the contamination of the plurality of electron emission tips 106 at one end of the tubular structure of the carbon nanotube obtained after the carbon nanotube preform is melted, and the mechanical mechanism of the carbon nanotube preform during heating. The strength will be increased to give it excellent field emission performance.
方法二：電子轟擊法，即首先加熱該管狀奈米碳管預製體，然後提供一電子發射源，使用該電子發射源轟擊該管狀奈米碳管預製體，使該管狀奈米碳管預製體在被轟擊處熔斷。方法二具體包括以下步驟：首先，加熱該管狀奈米碳管預製體。 Method 2: electron bombardment method, that is, first heating the tubular carbon nanotube preform, and then providing an electron emission source, using the electron emission source to bombard the tubular carbon nanotube preform to make the tubular carbon nanotube preform Blowed at the bombardment. The method 2 specifically includes the following steps: First, heating the tubular carbon nanotube preform.
將該管狀奈米碳管預製體放置於一真空系統。該真空系統的真空度維持1×10-4帕至1×10-5帕。在該管狀奈米碳管預製體中通入電流，加熱該管狀奈米碳管預製體至1800K至2500K。 The tubular carbon nanotube preform is placed in a vacuum system. The vacuum system maintains a vacuum of 1 x 10 -4 Pa to 1 x 10 -5 Pa. An electric current is introduced into the tubular carbon nanotube preform to heat the tubular carbon nanotube preform to 1800K to 2500K.
其次，提供一電子發射源，使用該電子發射源轟擊該管狀奈米碳管預製體，使該管狀奈米碳管預製體在被轟擊處熔斷。 Secondly, an electron emission source is provided, and the tubular carbon nanotube preform is bombarded with the electron emission source, so that the tubular carbon nanotube preform is blown at the bombardment.
提供一電子發射源，該電子發射源可採用奈米碳管線。將該電子發射源接入一低電位，該管狀奈米碳管預製體接入一高電位。將該電子發射源與該管狀奈米碳管預製體垂直放置，並使該電子發射源指向該管狀奈米碳管預製體被轟擊處。該電子發射源發射之電子束轟擊該管狀奈米碳管預製體的管壁，使該管狀奈米碳管預 製體被轟擊處的溫度升高。這樣一來，該管狀奈米碳管預製體被轟擊處具有最高的溫度。該管狀奈米碳管預製體會在該轟擊處熔斷，形成奈米碳管管狀結構，該奈米碳管管狀結構之一端形成複數電子發射尖端106。 An electron emission source is provided, and the electron emission source can be a carbon nanotube. The electron emission source is connected to a low potential, and the tubular carbon nanotube preform is connected to a high potential. The electron emission source is placed perpendicular to the tubular carbon nanotube preform, and the electron emission source is directed to the tubular carbon nanotube preform to be bombarded. An electron beam emitted from the electron emission source bombards a tube wall of the tubular carbon nanotube preform, so that the tubular carbon nanotube is pre-treated The temperature at which the body is bombarded increases. In this way, the tubular carbon nanotube preform has the highest temperature at the bombardment. The tubular carbon nanotube preform is melted at the bombardment to form a tubular structure of carbon nanotubes, one end of which forms a plurality of electron-emitting tips 106.
進一步的，上述電子發射源相對於該管狀奈米碳管預製體的具體定位，可以通過一操作臺來實現。其中，該電子發射源與該管狀奈米碳管預製體之間的距離為50微米至2毫米。本發明實施例優選將該管狀奈米碳管預製體固定到一可以實現三維移動的操作臺上。通過調節該管狀奈米碳管預製體在三維空間的移動，使該電子發射源與該管狀奈米碳管預製體在同一平面內並且互相垂直。該電子發射源與該管狀奈米碳管預製體之間的距離為50微米。 Further, the specific positioning of the electron emission source relative to the tubular carbon nanotube preform can be realized by a console. Wherein, the distance between the electron emission source and the tubular carbon nanotube preform is 50 micrometers to 2 millimeters. In an embodiment of the invention, the tubular carbon nanotube preform is preferably fixed to a station on which three-dimensional movement can be achieved. By adjusting the movement of the tubular carbon nanotube preform in three dimensions, the electron emission source is in the same plane and perpendicular to the tubular carbon nanotube preform. The distance between the electron emission source and the tubular carbon nanotube preform is 50 microns.
可以理解，為了提供更大的場發射電流以提高該管狀奈米碳管預製體局域的溫度，可以使用複數電子發射源同時提供場發射電流。進一步的，還可以使用其他形式的電子束來實現該管狀奈米碳管預製體的定點熔斷，比如傳統的熱陰極電子源發射的電子束或者其他常見場發射電子源發射的電子束。 It will be appreciated that in order to provide a greater field emission current to increase the temperature of the tubular carbon nanotube preform local, a plurality of electron emission sources may be used to simultaneously provide a field emission current. Further, other forms of electron beams can be used to achieve spot-spotting of the tubular carbon nanotube preform, such as an electron beam emitted by a conventional hot cathode electron source or an electron beam emitted by other common field emission electron sources.
方法三：鐳射照射法，即以一定功率及掃描速度的鐳射照射該管狀奈米碳管預製體，在該管狀奈米碳管預製體通入電流，該管狀奈米碳管預製體在被鐳射照射處熔斷，形成所述電子發射體10。方法三具體包括以下步驟：首先，以一定功率及掃描速度的鐳射照射該管狀奈米碳管預製體。 Method 3: a laser irradiation method, that is, irradiating the tubular carbon nanotube preform with a laser of a certain power and a scanning speed, and introducing a current into the tubular carbon nanotube preform, the tubular carbon nanotube preform being laser-injected The electron beam 10 is formed by melting at the irradiation place. The third method specifically includes the following steps: First, the tubular carbon nanotube preform is irradiated with laser light of a certain power and scanning speed.
將上述的管狀奈米碳管預製體放置於空氣或者含有氧化性氣體的 氣氛中。以一定功率及掃描速度之鐳射照射該管狀奈米碳管預製體。當該管狀奈米碳管預製體的某一位置被鐳射照射溫度升高後，空氣中的氧氣會氧化該位置處之奈米碳管，產生缺陷，從而使該位置處的電阻變大。 Place the above tubular carbon nanotube preform in air or contain an oxidizing gas In the atmosphere. The tubular carbon nanotube preform is irradiated with laser light of a certain power and scanning speed. When a position of the tubular carbon nanotube preform is raised by the laser irradiation temperature, oxygen in the air oxidizes the carbon nanotube at the position to cause a defect, thereby increasing the electric resistance at the position.
可以理解，鐳射照射該管狀奈米碳管預製體的時間及該鐳射的功率成反比。即鐳射功率較大時，鐳射照射該管狀奈米碳管預製體的時間較短；鐳射功率較小時，鐳射照射該管狀奈米碳管預製體的時間較長。 It will be appreciated that the time that the laser illuminates the tubular carbon nanotube preform is inversely proportional to the power of the laser. That is, when the laser power is large, the time for the laser to irradiate the tubular carbon nanotube preform is short; when the laser power is small, the laser irradiates the tubular carbon nanotube preform for a long time.
鐳射的功率為1瓦~60瓦，掃描速度為100-2000毫米/秒。優選的，鐳射的功率為12瓦，掃描速度為1000毫米/秒。鐳射可以係二氧化碳鐳射、半導體鐳射、紫外鐳射等任何形式的鐳射，只要能產生加熱的效果即可。 The laser power is 1 watt to 60 watts and the scanning speed is 100-2000 mm/sec. Preferably, the laser power is 12 watts and the scanning speed is 1000 mm/second. The laser can be any type of laser such as carbon dioxide laser, semiconductor laser, ultraviolet laser, etc., as long as it can produce heating effect.
其次，在該管狀奈米碳管預製體通入電流，管狀奈米碳管預製體在被鐳射照射處熔斷，形成二奈米碳管管狀結構，且奈米碳管管管狀結構的一端形成有複數電子發射尖端106。 Secondly, a current is applied to the tubular carbon nanotube preform, and the tubular carbon nanotube preform is melted by the laser irradiation to form a tubular structure of the carbon nanotubes, and one end of the tubular structure of the carbon nanotube tube is formed. A plurality of electron emission tips 106.
將經過鐳射照射後之管狀奈米碳管預製體放置於一真空系統中，該奈米碳管管狀結構二端分別與陽極接線柱及陰極接線柱電性連接後通入電流。該管狀奈米碳管預製體中被鐳射照射的部位係溫度最高的部位，最後該管狀奈米碳管預製體會在該處熔斷，形成二奈米碳管管狀結構。 The tubular carbon nanotube preform after laser irradiation is placed in a vacuum system, and the two ends of the tubular structure of the carbon nanotube are electrically connected to the anode terminal and the cathode terminal, respectively, and an electric current is supplied. The portion of the tubular carbon nanotube preform that is irradiated with laser light is the portion with the highest temperature, and finally the tubular carbon nanotube preform is melted there to form a tubular structure of two carbon nanotubes.
可以理解，還可將該管狀奈米碳管預製體設置於一真空或者充滿惰性氣體的氣氛中。該管狀奈米碳管預製體在被電流加熱的同時，以一定功率及掃描速度的鐳射照射該管狀奈米碳管預製體。由 於係真空或者惰性氣體的氣氛，故該管狀奈米碳管預製體可以被穩定地加熱。當該管狀奈米碳管預製體的某一位置被鐳射照射溫度升高後，該位置係溫度最高的部位，最後該管狀奈米碳管預製體會在該處燒斷。 It will be appreciated that the tubular carbon nanotube preform can also be placed in a vacuum or an atmosphere filled with an inert gas. The tubular carbon nanotube preform irradiates the tubular carbon nanotube preform with laser light of a certain power and scanning speed while being heated by current. by The tubular carbon nanotube preform can be stably heated in a vacuum or an inert gas atmosphere. When a position of the tubular carbon nanotube preform is raised by the laser irradiation temperature, the position is the highest temperature portion, and finally the tubular carbon nanotube preform is blown there.
由於管狀奈米碳管預製體二端分別固定於陽極接線柱與陰極接線柱，並且相鄰奈米碳管之間存在凡得瓦力，因此在熔斷的過程中，熔斷處的奈米碳管在遠離熔斷處並與之相鄰的奈米碳管的作用下，其螺旋方向逐漸趨向於延伸方向，即，奈米碳管的螺旋方向與所述延伸方向所形成的交叉角α逐漸接近於0°並分散，形成所述複數發散的電子發射尖端106。 Since the two ends of the tubular carbon nanotube preform are respectively fixed to the anode terminal and the cathode terminal, and the van der Waals force exists between adjacent carbon nanotubes, the carbon nanotube at the fuse is blown during the fusing process. Under the action of the carbon nanotubes away from the fuse and adjacent thereto, the spiral direction gradually tends to extend, that is, the intersection angle α formed by the spiral direction of the carbon nanotubes with the extending direction is gradually close to 0° and dispersed to form the plurality of diverging electron emission tips 106.
通過上述三種熔斷管狀奈米碳管預製體的方法得到的電子發射體10中的奈米碳管的質量得到了極大的提高。這一方面係由於奈米碳管經過熱處理後缺陷減少，另一方面係因為富含缺陷的石墨層容易在高溫下崩潰，剩下一些質量較高的石墨層。本實施例中採用電流熔斷法熔斷上述管狀奈米碳管預製體。 The quality of the carbon nanotubes in the electron emitter 10 obtained by the above three methods of fusing a tubular carbon nanotube preform is greatly improved. This is due to the reduced defects of the carbon nanotubes after heat treatment, and the fact that the graphite layer rich in defects is liable to collapse at high temperatures, leaving some higher quality graphite layers. In the embodiment, the tubular carbon nanotube preform is melted by a current fusing method.
本發明第一實施例提供的電子發射體10的製備方法具有如下優點：其一，該種電子發射體10之製備方法簡單，可以提高電子發射體10的製備效率；其二，通過熔斷的方法使管狀奈米碳管預製體熔斷後得到的奈米碳管管狀結構的一端形成有複數電子發射尖端106，進而使該奈米碳管管狀結構具有較好的電子發射性能。 The method for preparing the electron emitter 10 provided by the first embodiment of the present invention has the following advantages: First, the preparation method of the electron emitter 10 is simple, and the preparation efficiency of the electron emitter 10 can be improved; and second, the method of fusing One end of the tubular structure of the carbon nanotube obtained after the tubular carbon nanotube preform is melted is formed with a plurality of electron emission tips 106, thereby making the carbon nanotube tubular structure have better electron emission performance.
請參閱圖8，本發明第二實施例提供一種電子發射體20及其製備方法。所述電子場發射體20包括一奈米碳管複合線狀結構。所述奈米碳管複合線狀結構包括一導電線狀結構220及一奈米碳管層210設置於所述導電線狀結構220的表面，所述奈米碳管層210環 繞所述導電線狀結構220形成一奈米碳管管狀結構，在所述奈米碳管複合線狀結構的一端，所述奈米碳管管狀結構伸出複數電子發射尖端206。所述奈米碳管複合線狀結構具有複數電子發射尖端206的一端為類圓錐形，作為電子發射部212。具體地，所述導電線狀結構220的整個表面被所述奈米碳管層210包覆。該奈米碳管管狀結構的長度大於所述導電線狀結構220的長度。所述奈米碳管層210為至少一自支撐的奈米碳管膜或奈米碳管線纏繞在所述導電線狀結構220的表面形成。本發明第二實施例提供的電子發射體20的結構同第一實施例提供的電子發射體10的結構基本相同，所述電子發射體20中奈米碳管層210形成的奈米碳管管狀結構與所述電子發射體10中的奈米碳管管狀結構完全相同。其區別在於：電子發射體20進一步包括一導電線狀結構220設置於該奈米碳管管狀結構的內部。即，所述導電線狀結構220設置於所述奈米碳管管狀結構的中空的線狀軸心的位置，並取代了中空的線狀軸心。 Referring to FIG. 8, a second embodiment of the present invention provides an electron emitter 20 and a method of fabricating the same. The electron field emitter 20 includes a carbon nanotube composite wire structure. The carbon nanotube composite linear structure includes a conductive linear structure 220 and a carbon nanotube layer 210 disposed on a surface of the conductive linear structure 220, and the carbon nanotube layer 210 is ring-shaped. A carbon nanotube tubular structure is formed around the electrically conductive linear structure 220. At one end of the carbon nanotube composite linear structure, the carbon nanotube tubular structure protrudes from the plurality of electron emission tips 206. The carbon nanotube composite linear structure having one end of the complex electron emission tip 206 is a conical shape as the electron emission portion 212. Specifically, the entire surface of the conductive linear structure 220 is covered by the carbon nanotube layer 210. The length of the carbon nanotube tubular structure is greater than the length of the electrically conductive linear structure 220. The carbon nanotube layer 210 is formed by winding at least one self-supporting carbon nanotube film or a nano carbon line on the surface of the conductive linear structure 220. The structure of the electron emitter 20 provided by the second embodiment of the present invention is substantially the same as that of the electron emitter 10 provided by the first embodiment, and the carbon nanotube tube 210 formed by the carbon nanotube layer 210 in the electron emitter 20 is tubular. The structure is identical to the tubular structure of the carbon nanotubes in the electron emitter 10. The difference is that the electron emitter 20 further includes a conductive linear structure 220 disposed inside the tubular structure of the carbon nanotube. That is, the conductive linear structure 220 is disposed at a position of a hollow linear axis of the tubular structure of the carbon nanotubes, and replaces a hollow linear axis.
所述導電線狀結構220具有支撐所述奈米碳管管狀結構的作用，所以該導電線狀結構220應具有一定的強度及韌性。導電線狀結構220的材料可為單質金屬，所述單質金屬材料可為金、銀、銅或鋁等金屬材料。所述導電線狀結構220的材料也可為金屬合金材料，如銅錫合金。所述導電線狀結構220的材料還可為碳纖維等導電的非金屬材料或導電的金屬氧化物等。所述導電線狀結構220還可為具有一導電層之複合線狀結構，如在銅錫合金表面進一步塗覆一層鋁膜；還可以在一柔性材料如纖維絲的表面鍍金膜。所述導電線狀結構220的直徑不限，只要該導電線狀結構220具有一定強度即可。優選地，所述導電線狀結構220的直徑範圍為 10微米到30微米。當導電線狀結構220為鋁絲，該鋁絲的直徑可為25微米。本實施例中，該導電線狀結構220為金絲，該金絲的直徑可為18微米。 The electrically conductive linear structure 220 has the function of supporting the tubular structure of the carbon nanotubes, so the electrically conductive linear structure 220 should have a certain strength and toughness. The material of the conductive linear structure 220 may be an elemental metal, and the elemental metal material may be a metal material such as gold, silver, copper or aluminum. The material of the conductive linear structure 220 may also be a metal alloy material such as a copper-tin alloy. The material of the conductive linear structure 220 may also be a conductive non-metal material such as carbon fiber or a conductive metal oxide or the like. The conductive linear structure 220 may also be a composite linear structure having a conductive layer, such as further coating an aluminum film on the surface of the copper-tin alloy; or plating a gold film on the surface of a flexible material such as a fiber. The diameter of the conductive linear structure 220 is not limited as long as the conductive linear structure 220 has a certain strength. Preferably, the diameter of the conductive linear structure 220 ranges from 10 microns to 30 microns. When the electrically conductive wire structure 220 is an aluminum wire, the aluminum wire may have a diameter of 25 microns. In this embodiment, the conductive linear structure 220 is a gold wire, and the gold wire may have a diameter of 18 micrometers.
本發明第二實施例提供的電子發射體20的奈米碳管管狀結構中設置有一導電線狀結構220，該導電線狀結構220可支撐所述奈米碳管管狀結構，使奈米碳管管狀結構不易變形，且該導電線狀結構220可使電子發射體20之導電性增加，使電子發射體20更易於發射電子。 In the tubular structure of the carbon nanotubes of the electron emitter 20 provided by the second embodiment of the present invention, a conductive linear structure 220 is disposed, and the conductive linear structure 220 can support the tubular structure of the carbon nanotubes to make the carbon nanotubes The tubular structure is not easily deformed, and the conductive linear structure 220 can increase the conductivity of the electron emitter 20, making it easier for the electron emitter 20 to emit electrons.
本發明第二實施例提供該電子發射體20之製備方法，其包括以下步驟：步驟S201，提供一導電線狀結構220，及至少一奈米碳管膜或至少一奈米碳管線。步驟S202，將所述至少一奈米碳管膜或至少一奈米碳管線纏繞在所述導電線狀結構220表面形成一奈米碳管複合線狀結構。步驟S203，熔斷所述奈米碳管複合線狀結構得到電子發射體20。 A second embodiment of the present invention provides a method for fabricating the electron emitter 20, which includes the following steps: Step S201, providing a conductive linear structure 220, and at least one carbon nanotube film or at least one nano carbon line. Step S202, winding the at least one carbon nanotube film or at least one nano carbon line on the surface of the conductive linear structure 220 to form a carbon nanotube composite linear structure. In step S203, the carbon nanotube composite linear structure is melted to obtain an electron emitter 20.
本發明第二實施例提供的電子發射體20的製備方法與本發明第一實施例提供的電子發射體10的製備方法相似，其中，所述奈米碳管膜或者奈米碳管線在所述導電線狀結構220上的纏繞方式、及所述奈米碳管複合線狀結構的熔斷方式與第一實施例相同，其區別在於，(1)第二實施例採用導電線狀結構220替代第一實施例中的線狀支撐體，所述至少一奈米碳管膜或至少一奈米碳管線纏繞在所述導電線狀結構220的表面；(2)在熔斷前無需移除所述導電線狀結構220的步驟。 The method for preparing the electron emitter 20 according to the second embodiment of the present invention is similar to the method for preparing the electron emitter 10 according to the first embodiment of the present invention, wherein the carbon nanotube film or the carbon nanotube line is in the The winding manner on the conductive linear structure 220 and the melting manner of the carbon nanotube composite linear structure are the same as those in the first embodiment, and the difference is that (1) the second embodiment uses the conductive linear structure 220 instead of the first embodiment. In the embodiment of the linear support, the at least one carbon nanotube film or at least one nano carbon line is wound around the surface of the conductive linear structure 220; (2) the conductive is not removed before the fusing The step of the linear structure 220.
在熔斷的過程中，設置於奈米碳管管狀結構內部之導電線狀結構220在電流的作用下，或者在電子束、鐳射及電流的共同作用下 ，該導電線狀結構220及奈米碳管管狀結構處於很高的溫度。當溫度達到一定程度，導電線狀結構220及奈米碳管管狀結構中熔點較低之一將會首先熔斷。若導電線狀結構220首先熔斷，則奈米碳管管狀結構中與導電線狀結構220對應的一點的電阻將會迅速升高，溫度迅速升高，從而使奈米碳管管狀結構及導電線狀結構220在同一點熔斷。若奈米碳管管狀結構先熔斷，則導電線狀結構220中與奈米碳管管狀結構相對應的一點的電阻將會迅速升高，溫度迅速升高，從而使導電線狀結構220也在該點熔斷，最終導電線狀結構220及奈米碳管管狀結構在同一點熔斷。當所述導電線狀結構220為金屬材料時，在熔斷的過程中，金屬原子發生蒸發，從而使熔斷後的奈米碳管管狀結構的縮口部份內的金屬不存在。 During the fusing process, the electrically conductive linear structure 220 disposed inside the tubular structure of the carbon nanotube is under the action of current or electron beam, laser and current. The conductive linear structure 220 and the carbon nanotube tubular structure are at a very high temperature. When the temperature reaches a certain level, one of the lower melting points of the conductive linear structure 220 and the tubular structure of the carbon nanotube will be first melted. If the conductive linear structure 220 is first melted, the resistance of the carbon nanotube tubular structure corresponding to the conductive linear structure 220 will rapidly increase, and the temperature rapidly rises, thereby making the carbon nanotube tubular structure and the conductive wire. The structure 220 is blown at the same point. If the tubular structure of the carbon nanotube is first melted, the resistance of the conductive linear structure 220 corresponding to the tubular structure of the carbon nanotube will rapidly increase, and the temperature rapidly rises, so that the conductive linear structure 220 is also The spot is blown, and finally the conductive linear structure 220 and the carbon nanotube tubular structure are blown at the same point. When the conductive linear structure 220 is a metal material, metal atoms are evaporated during the fusing process, so that the metal in the constricted portion of the blown carbon nanotube tubular structure is not present.
本發明第二實施例提供的電子發射體20之製備方法具有以下優點：其一，該方法簡單，可以提高電子發射體20之製備效率；其二，通過熔斷的方法使奈米碳管複合線狀結構熔斷後得到的電子發射體20之一端形成有複數電子發射尖端206，進而使電子發射體20具有較好之電子發射性能；其三，奈米碳管複合線狀結構內部設置有一導電線狀結構220，該導電線狀結構220可支撐所述奈米碳管管狀結構，使奈米碳管複合線狀結構不易變形；其四，導電線狀結構220可使電子發射體20之導電性增加，使電子發射體20更易於發射電子。 The method for preparing the electron emitter 20 provided by the second embodiment of the present invention has the following advantages: First, the method is simple, and the preparation efficiency of the electron emitter 20 can be improved; and second, the carbon nanotube composite line is formed by a fuse method. A plurality of electron-emitting tips 206 are formed at one end of the electron-emitting body 20 obtained by melting the structure, so that the electron-emitting body 20 has better electron-emitting properties; and third, a conductive line is disposed inside the carbon nanotube composite linear structure. The conductive structure 220 can support the tubular structure of the carbon nanotubes, so that the carbon nanotube composite linear structure is not easily deformed; and fourth, the conductive linear structure 220 can make the electron emitter 20 conductive. The increase makes it easier for the electron emitter 20 to emit electrons.
請參閱圖9，本發明第三實施例提供一種電子發射元件30，包括：一導電基體34；及至少一電子發射體32。所述電子發射體32與所述導電基體34電連接，所述電子發射體32具有複數電子發射尖 端306的一端沿遠離所述導電基體34之方向延伸。 Referring to FIG. 9, a third embodiment of the present invention provides an electron emitting device 30, including: a conductive substrate 34; and at least one electron emitter 32. The electron emitter 32 is electrically connected to the conductive substrate 34, and the electron emitter 32 has a plurality of electron emission tips. One end of the end 306 extends in a direction away from the conductive substrate 34.
所述電子發射體32可為本發明第一實施例中的電子發射體10或第二實施例中之電子發射體20。 The electron emitter 32 may be the electron emitter 10 in the first embodiment of the invention or the electron emitter 20 in the second embodiment.
該導電基體34由導電材料製成，如銅、鎢、金、鉬或鉑等。該導電基體34可依實際需要設計成其他形狀，如錐形、細小的柱形或者圓臺形。該導電基體34也可為形成在一絕緣基底上的導電薄膜。在具體應用中，所述導電基體34可為電子發射裝置中之陰極電極，用以提供電壓給所述電子發射體32。 The conductive substrate 34 is made of a conductive material such as copper, tungsten, gold, molybdenum or platinum. The conductive substrate 34 can be designed into other shapes according to actual needs, such as a cone shape, a small column shape or a truncated cone shape. The conductive substrate 34 can also be a conductive film formed on an insulating substrate. In a particular application, the conductive substrate 34 can be a cathode electrode in an electron-emitting device for providing a voltage to the electron emitter 32.
可以理解，該電子發射體32之一端可以通過一導電膠與該導電基體34電連接。該電連接的方式也可以通過分子間力或者其他方式實現。該電子發射體32與導電基體34之間的位置關係不限，只需確保該電子發射體32的一端與該導電基體34電連接即可。如電子發射體32與導電基體34的夾角為銳角，電子發射體32與導電基體34的夾角為直角或者電子發射體32與導電基體34的軸向相互平行。當所述電子發射體30為32上述第二實施例中的電子發射體20時，所述電子發射體32包括一導電線狀結構，該導電線狀結構可以與所述導電基體34直接電性接觸以實現電子發射體32與所述導電基體34的電連接。所述導電線狀結構可直接焊接在所述導電基體34的表面或與所述導電基體34一體成型設置。所述電子發射體32通過所述導電線狀結構固定並與所述導電基體34電性連接。 It can be understood that one end of the electron emitter 32 can be electrically connected to the conductive substrate 34 through a conductive paste. The manner of electrical connection can also be achieved by intermolecular forces or other means. The positional relationship between the electron emitter 32 and the conductive substrate 34 is not limited, and it is only necessary to ensure that one end of the electron emitter 32 is electrically connected to the conductive substrate 34. For example, the angle between the electron emitter 32 and the conductive substrate 34 is an acute angle, the angle between the electron emitter 32 and the conductive substrate 34 is a right angle, or the electron emitter 32 and the conductive substrate 34 are parallel to each other in the axial direction. When the electron emitter 30 is the electron emitter 20 in the second embodiment described above, the electron emitter 32 includes a conductive line structure, and the conductive line structure can be directly electrically connected to the conductive substrate 34. Contact to achieve electrical connection of the electron emitter 32 to the conductive substrate 34. The conductive wire structure may be directly soldered to the surface of the conductive substrate 34 or integrally formed with the conductive substrate 34. The electron emitter 32 is fixed by the conductive linear structure and electrically connected to the conductive substrate 34.
另外，所述電子發射元件30可包括複數電子發射體32與所述導電基體34的電性連接，所述複數電子發射體32的一端均與導電基體34的電性連接。所述複數電子發射體32的設置可有效增加所述電子發射元件30的發射電流密度。所述複數電子發射體32具體設置 方式不限，如相互平行且間隔設置、並排設置或交叉設置等。 In addition, the electron-emitting element 30 may include an electrical connection between the plurality of electron emitters 32 and the conductive substrate 34, and one end of the plurality of electron emitters 32 is electrically connected to the conductive substrate 34. The arrangement of the plurality of electron emitters 32 can effectively increase the emission current density of the electron-emitting elements 30. The plurality of electron emitters 32 are specifically set The method is not limited, such as parallel to each other and spaced apart, side by side setting or cross setting.
在應用時，通過所述導電基體34實現該電子發射元件32與其他元件之間的電連接。 In use, the electrical connection between the electron-emitting element 32 and the other elements is achieved by the electrically conductive substrate 34.
本發明第三實施例提供的電子發射元件30具有以下有益效果：其一，由於電子發射體32包括複數電子發射尖端，因此電子發射體32具有較大的發射電流；其二，所述奈米碳管管狀結構之一端延伸出複數電子發射尖端306，因此，可有效降低該電子發射體32的電場屏蔽效應；其三，所述複數電子發射尖端306的尖端狀可增強電子發射體32的場增強因子，使電子發射體32更易於發射電子，從而提高電子發射體32的場發射性能；其四，所述電子發射元件30包括一導電基體32，當所述電子發射元件30在應用時，通過該導電基體32可以實現該導電基體32更好地與其他元件電連接。 The electron-emitting element 30 provided by the third embodiment of the present invention has the following advantageous effects: First, since the electron emitter 32 includes a plurality of electron-emitting tips, the electron-emitting body 32 has a large emission current; and second, the nano-particle One end of the carbon tube tubular structure extends out of the complex electron emission tip 306, thereby effectively reducing the electric field shielding effect of the electron emitter 32. Third, the tip end of the complex electron emission tip 306 can enhance the field of the electron emitter 32. The enhancement factor makes the electron emitter 32 easier to emit electrons, thereby improving the field emission performance of the electron emitter 32. Fourth, the electron emission element 30 includes a conductive substrate 32, when the electron emission element 30 is in use, The conductive substrate 32 can be electrically connected to other components by the conductive substrate 32.
綜上所述，本發明確已符合發明專利之要件，遂依法提出專利申請。惟，以上所述者僅為本發明之較佳實施例，自不能以此限制本案之申請專利範圍。舉凡熟悉本案技藝之人士援依本發明之精神所作之等效修飾或變化，皆應涵蓋於以下申請專利範圍內。 In summary, the present invention has indeed met the requirements of the invention patent, and has filed a patent application according to law. However, the above description is only a preferred embodiment of the present invention, and it is not possible to limit the scope of the patent application of the present invention. Equivalent modifications or variations made by persons skilled in the art in light of the spirit of the invention are intended to be included within the scope of the following claims.
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| CN1941249A (en) * | 2005-09-30 | 2007-04-04 | 清华大学 | Field transmitter and its production |
| US20070145878A1 (en) * | 2005-12-23 | 2007-06-28 | Tsinghua University | Field emission illumination device |
| CN101425435A (en) * | 2007-11-02 | 2009-05-06 | 清华大学 | Field emission type electron source and its manufacturing method |
| US20090134772A1 (en) * | 2007-11-23 | 2009-05-28 | Tsinghua University | Color field emission display having carbon nanotubes |
| US20100055338A1 (en) * | 2008-08-26 | 2010-03-04 | Snu R&Db Foundation | Carbon nanotube structure |
| TWI327177B (en) * | 2007-02-12 | 2010-07-11 | Hon Hai Prec Ind Co Ltd | Carbon nanotube film and method for making same |
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|---|---|---|---|---|
| CN1941249A (en) * | 2005-09-30 | 2007-04-04 | 清华大学 | Field transmitter and its production |
| US20070145878A1 (en) * | 2005-12-23 | 2007-06-28 | Tsinghua University | Field emission illumination device |
| TWI327177B (en) * | 2007-02-12 | 2010-07-11 | Hon Hai Prec Ind Co Ltd | Carbon nanotube film and method for making same |
| CN101425435A (en) * | 2007-11-02 | 2009-05-06 | 清华大学 | Field emission type electron source and its manufacturing method |
| US20090134772A1 (en) * | 2007-11-23 | 2009-05-28 | Tsinghua University | Color field emission display having carbon nanotubes |
| US20100055338A1 (en) * | 2008-08-26 | 2010-03-04 | Snu R&Db Foundation | Carbon nanotube structure |
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