CN1135588C - Method of raising the field electron emitting performance of carbon nanotube film - Google Patents
Method of raising the field electron emitting performance of carbon nanotube film Download PDFInfo
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- CN1135588C CN1135588C CNB01132287XA CN01132287A CN1135588C CN 1135588 C CN1135588 C CN 1135588C CN B01132287X A CNB01132287X A CN B01132287XA CN 01132287 A CN01132287 A CN 01132287A CN 1135588 C CN1135588 C CN 1135588C
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y10/00—Nanotechnology for information processing, storage or transmission, e.g. quantum computing or single electron logic
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J9/00—Apparatus or processes specially adapted for the manufacture, installation, removal, maintenance of electric discharge tubes, discharge lamps, or parts thereof; Recovery of material from discharge tubes or lamps
- H01J9/02—Manufacture of electrodes or electrode systems
- H01J9/022—Manufacture of electrodes or electrode systems of cold cathodes
- H01J9/025—Manufacture of electrodes or electrode systems of cold cathodes of field emission cathodes
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Abstract
The present invention provides a method for raising the field electron emitting performance of a nanometer carbon tube film, which belongs to the field of field emitting displayers. The present invention is characterized in that a CNT film cathode which is prepared by a transplant method adopts a heat treating technology and a plasma volume surface treating technology, but a CNT film cathode which is prepared by a direct growing method only adopts a plasma surface treating technology. The plasma surface treatment has technology parameters that the power density is 0.1 to 3 W/cm<3>, the treating time is 5 to 60 minutes, and H2 or hydrogen-containing compounds are used. Being treated by the method provided by the present invention, the current density of the CNT film is improved to three times, the strength of the threshold value is reduced more than three times, the density of electric emitting points can be raised more than three orders of magnitudes, and the uniformity is improved obviously. A film cathode grown by the transplant method is treated by the organic combination of the two technologies to generally improve the field emitting performance of the CNT film cathode.
Description
Technical field
The present invention relates to the method for the electronic emission performance of a kind of raising carbon nano-tube (CNT) film, the method that combines by Technology for Heating Processing and plasma surface treatment craft more precisely makes a kind of method that the electronic emission performance of CNT film is significantly improved.Belong to the Field Emission Display field.
Background technology
In recent years, an emission becomes a very active field.Consistently in the world think that Field Emission Display (FED) has broad prospects and future in flat panel display market.Compare with LCD, the various performances of Field Emission Display are leading comprehensively, advantages such as simplification with high brightness, more good view effect, low-power consumption, the size of dwindling greatly, manufacture craft, therefore be described as the Display Technique (K.Derbyshire of 21st century, Solid State Technol.38,71 (1995); J.Roberston, Thin Solid Films 296,62 (1997)).Wherein cold-cathode material is the core component of Field Emission Display.Metal M o is contaminated easily, and impurity can make the surface work function of Mo increase in absorption or its reaction on its surface, reduces the electronic field emission performance.The poor mechanical property of while Mo, the useful life of shortening material.Si is a kind of quite crisp material, and heat conductivility is poor simultaneously.Obviously, along with the rapid emergence of Field Emission Display, it is unable to do what one wishes that traditional field emmision material has seemed.Nowadays, the making of FED is that Spindt (Mo pointed cone) method of using with French PixTech company is a main flow, yet this method requires large-area accurate micromachined, and cost rises significantly, so limited its competitiveness.At present, the world emission area research the most popular cold-cathode material of entering the court is CNT (D.Normile, " Nanotubes Generate Full-Color Displays ", Science, 286,2056, (1998); W.B.Choi, N.S.Lee, W.K.Yi, Y.W.Jin, Y.S.Choi, L.T.Han, D.S.Chung, H.Y.Kim, J.H.Kang, J.H.You, and J.M.Kim, SID 00 Digest, 324, (2000)).The CNT general diameter is a few to tens of nanometers, and length is several microns, and so shape makes CNT may produce an enough big field enhancement factor under certain electric field strength, thereby obtains the good electron emitting performance.Simultaneously, CNT has very high intensity, good thermal conductivity and chemical stability, thereby is a kind of very desirable field emission cold-cathode material.
The preparation of CNT cathode thin film array has two kinds of methods usually: a kind of is the direct growth method; A kind of is grafting.The CNT of direct growth method growth and substrate good bonding strength, purity height, but growth temperature is generally higher make CNT be grown in that (practicability requirement) has certain technical difficulty on the glass substrate, and are unfavorable for large area deposition, and efficient is low, the cost height.And the advantage of grafting is high efficiency, low cost, can prepares large-area negative electrode, thereby many in the world major companies, as ISES (S.Uemura, SID 00Digest, 320-323 (2000)), Samsung (W.B.Choi, SID 00 Digest, 324-327 (2000)), and ERSO/ITRI (F.Y.Chuang, SID 00 Digest, 329-331 (2000)) adopts grafting to prepare the negative electrode of Field Emission Display.Grafting is to make FED move towards a kind of desirable technique of practicability, industrialization.Current, two kinds of methods all will pursue one's goal and fix on aspects such as hanging down work field intensity, high current density, high dot density, even emission.The application prospect of grafting is more tempting.
Summary of the invention
The object of the present invention is to provide a kind of simple but effective method to improve the electronic emission performance of CNT film, be embodied in the reduction of the threshold field of electronics emission, the raising of emission, the raising of the dot density of electronics emission and four aspects of inhomogeneity improvement of emission.
Method provided by the invention is primarily aimed at the CNT film cathode of grafting preparation.At first, by the organic additive in the Technology for Heating Processing removal migration process, the content of amorphous carbon (a-C) and graphitic carbon (G-C) among the reduction CNT, form Mechanical Contact good between CNT and substrate and electrically contact, then again by the further clean surface of plasma surface treatment craft, reduce surface work function, thereby the electronic emission performance of CNT film is significantly improved.The field emission electron performance methodology of raising CNT film also provided by the invention in other words is to realize by the method that heat treatment and two technologies of plasma surface treatment are complementary.
The grafting of the preparation CNT film cathode of mentioning among the present invention is meant: at first, prepare the CNT powder with various distinct methods, the CNT powder is ined all sorts of ways transfer on the different backing materials then, obtain the CNT film cathode.The method for preparing the CNT powder comprises the CVD method of the glow discharge of direct-current arc discharge, various frequency ranges, laser flash method (Laser Ablation), heated filament CVD method, evaporation, catalytic pyrolysis method etc.; Transfer method comprises silk screen print method, rotation coating-exposure-development method etc.; Backing material comprises materials such as glass, metal, alloy, silicon chip, pottery.Film thickness is 10-60 μ, and the key that improves CNT thin film field electron emitting performance is the purifying of CNT and improves dispersed.Usually adopt grafting all can add organic gel and so on to the harmful material of field emission, so the primary and foremost purpose of treatment process is thoroughly to remove this class additive among the CNT before transplanting.Treatment process of the present invention mainly in two ways the technological parameter mode that is complementary carry out i.e. Technology for Heating Processing and plasma surface treatment craft.The former can be at 300-700 ℃, O
2-N
2Or H
2-N
2In carry out O
2Or H
2Flow account for the 3%-20% of total flow, purpose is to remove additive, reduces the content of a-C and G-C, forms Mechanical Contact good between CNT and substrate and electrically contacts.The purpose of plasma surface treatment is to be further purified again, makes the nearly surface portion of CNT reach best purification effect, reduces surface work function, thereby improves the dispersiveness of surface C NT.Plasma surface treatment can adopt the equipment of various generation plasmas to realize, as equipment such as capacitive coupling type, inductance coupling high type, microwave plasmas.Process conditions are plasma power density 0.1-3W/cm
3, plasma sheath shell voltage 100-500V; Operating air pressure 0.1-5 torr; Processing time 5-60 minute.The gas that adopts is hydrogen (H
2) or be the hydrogen-containing compound such as the ammonia (NH of gaseous state
3), methane (CH
4), ethene (C
2H
4), acetylene (C
2H
2) in a kind of, flow is the 10-100 ml/min.
CNT film cathode for the preparation of direct growth method, can omit Technology for Heating Processing and only adopt plasma surface treatment craft among the present invention to improve the electronic emission performance of CNT film, because the CNT film cathode of direct growth method preparation does not contain organic impurities, do not need the heat treatment organic impurities that volatilizees.All the other gas ions process of surface treatment are with the CNT film cathode of above-mentioned grafting growing and preparing.
The method that the present invention combines by Technology for Heating Processing and process of surface treatment, improve the electronic emission performance of the CNT film of grafting or direct growth method preparation, be mainly reflected under the same field intensity, can make the current density of CNT film improve about 3 times, threshold field strength has reduced more than 3 times, and the dot density of electronics emission can improve more than 3 orders of magnitude and uniformity obviously improves.If only adopt Technology for Heating Processing can only improve current density, can not significantly reduce threshold field strength and improve dot density; If only the using plasma treatment process can reduce threshold field strength and improve dot density to a certain extent, but can not significantly improve current density.The present invention has improved the field emission performance of the CNT film cathode of grafting preparation by the combination of two kinds of treatment process comprehensively.
Description of drawings
Fig. 1 is the electronic emission performance testing apparatus schematic diagram of the CNT film cathode after method provided by the invention is handled.Wherein: the 1-transparent glass sheet; The 2-indium-tin oxide electrode; The 3-low-voltage phosphor; The 4-insulated column that insulate; The 5-CNT film; The 6-backing material.
CNT film cathode after Fig. 2 adopts the present invention to handle and do not adopt the current density-electric field strength curve of the field-causing electron emission of the CNT film cathode that the present invention handles, wherein abscissa is electric field strength (V/ μ m), ordinate is current density (mA/cm
2).▲ and ■ represented respectively after adopting method of the present invention to handle and without the CNT film sample of any processing.
Fig. 3 is two phosphor screen luminous photos under the different disposal condition, Fig. 3 (a) is that Fig. 3 (b) is the CNT film cathode field emitted fluorescence screen luminous photo after handling through method of the present invention not through the CNT film cathode field emitted fluorescence screen luminous photo of any processing.
Embodiment
Test having adopted the present invention to handle with the electronic emission performance of the CNT film cathode that does not adopt the present invention to handle.The CNT film cathode that adopts adopts the silk screen print method preparation, and backing material is metallic nickel (Ni), and the CNT film thickness is about 40 μ m, and effective area is 10mm * 10mm.The sample of test be respectively the CNT film that do not pass through any processing and by the inventive method through the CNT of Overheating Treatment and plasma surface treatment film.The Technology for Heating Processing condition that adopts in the present embodiment is 600 ℃; H
2-N
2Protective gas, H
2Flow is 0.2 liter/minute, N
2Flow is 2 liters/minute; 10 minutes processing times.The plasma surface processor that present embodiment adopts is the capacitive coupling plasma etching apparatus.Process conditions are: plasma power density 0.275W/cm
3, plasma sheath shell voltage 215V; Logical hydrogen, gas flow 20 ml/min; Operating air pressure 0.4 torr; 20 minutes processing times; Room temperature.By being applied voltage, indium-tin oxide anode produces electric field.Under certain electric field, electronics effusion film surface with certain energy impact fluorescence powder, thereby produces fluorescence.The demonstration of fluorescence can reflect the uniformity of electronics emission intuitively.Test shows to the electronic emission performance of above-mentioned CNT film cathode: when electric field strength was 10.4V/ μ m, the electronic field emission current density of the CNT film cathode after handling by the inventive method was 6.84mA/cm
2, improved nearly 3 times of (2.58mA/cm than the CNT film cathode of not passing through any processing under the identical electric field strength
2); Threshold field strength is that 1.375V/ μ m is (in the present embodiment, threshold field strength is defined as under the identical condition of specimen area, added electric field strength when detecting 1 μ A electric current), the CNT film cathode than the not any processing of process has reduced (4.725V/ μ m) more than 3 times; The dot density and the uniformity of emission have been improved simultaneously significantly, as shown in Figure 3.Fig. 3 is one group of phosphor screen luminous photo under the different disposal condition, and Fig. 3 (a) is the CNT film cathode field emitted fluorescence screen luminous photo that does not pass through any processing under the electric field strength of 6.68V/ μ m, and launch point density is about 10
3Individual/cm
2, Fig. 3 (b) shields luminous photo through the CNT film cathode field emitted fluorescence after the method processing of the present invention under same electric field intensity, and launch point density is about 10
6Individual/cm
2, dot density has improved nearly 3 orders of magnitude, makes the electronic emission performance of CNT film cathode reach the requirement of practicability.
Test having adopted the present invention to handle with the electronic emission performance of the CNT film cathode that does not adopt the present invention to handle.The CNT film cathode employing silk screen print method preparation of adopting, backing material are the glass of layer of metal Ti of having grown, and electron beam evaporation method is adopted in the growth of metal Ti, and thickness is 500nm, and the CNT film thickness is about 40 μ m, and effective area is 10mm * 10mm.The sample of test be respectively the CNT film that do not pass through any processing and by the inventive method through the CNT of Overheating Treatment and plasma surface treatment film.Treatment process condition is with embodiment 1.Treatment effect is similar to embodiment 1.
Test having adopted the present invention to handle with the electronic emission performance of the CNT film cathode that does not adopt the present invention to handle.The CNT film cathode that adopts adopts the silk screen print method preparation, and backing material is silicon chip (Si), and the CNT film thickness is about 60 μ m, and effective area is 10mm * 10mm.The sample of test be respectively the CNT film that do not pass through any processing and by the inventive method through the CNT of Overheating Treatment and plasma surface treatment film.The Technology for Heating Processing condition that adopts in the present embodiment is 550 ℃; O
2-N
2Protective gas, O
2Flow is 0.1 liter/minute, N
2Flow is 2 liters/minute; 10 minutes processing times.The plasma surface processor that present embodiment adopts is the capacitive coupling plasma etching apparatus.Process conditions are: plasma power density 0.275W/cm
3, plasma sheath shell voltage 215V; Logical ammonia, gas flow 30 ml/min; Operating air pressure 0.8 torr; 30 minutes processing times; Room temperature.Treatment effect is similar to embodiment 1.
Test having adopted the present invention to handle with the field-causing electron field emission performance of the CNT film cathode that does not adopt the present invention to handle.The CNT film cathode that adopts is the preparation of direct growth method, and backing material is silicon chip (Si), and the CNT film thickness is about 10 μ m, and effective area is 5mm * 5mm.The sample of test is respectively not through the CNT film of any processing with by the CNT film of the inventive method through plasma surface treatment.The plasma surface processor that present embodiment adopts is the capacitive coupling plasma etching apparatus.Process conditions are: plasma power density 0.3W/cm
3, plasma sheath shell voltage 170V; Logical hydrogen, gas flow 30 ml/min; Operating air pressure 1 torr; 10 minutes processing times; Room temperature.The field emission of the CNT film cathode after the plasma treatment slightly improves, and threshold field is reduced to 1/2 of untreated samples, and launch point density has the raising of nearly two orders of magnitude.All the other are with embodiment 1.
Claims (2)
1, a kind of method that improves the electronic emission performance of carbon nano-tube film is characterized in that the CNT film cathode that grafting prepares, and adopts Technology for Heating Processing and plasma surface treatment craft; The temperature of described Technology for Heating Processing is 300-700 ℃, O
2-N
2Or H
2-N
2Carry out in the atmosphere; Described Surface Treatment with Plasma technology power density 0.1-3W/cm
3Plasma sheath shell voltage 100-500V; Operating air pressure 0.1-5 torr; Processing time 5-60 minute; The gas that adopts is H
2Or be the hydrogen-containing compound of gaseous state, be the 10-100 ml/min as a kind of flow in ammonia, methane, ethene, the acetylene.
2, press the method for the electronic emission performance of the described raising carbon nano-tube film of claim 1, it is characterized in that heat treatment is at O
2-N
2O when carrying out in the atmosphere
20.1 liter/minute of flow, N
22 liters/minute of flows are at H
2-N
2H when carrying out in the atmosphere
2Flow is 0.2 liter/minute, N
2Flow is 2 liters/minute; Processing time is 10 minutes.
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|---|---|---|---|
| CNB01132287XA CN1135588C (en) | 2001-11-23 | 2001-11-23 | Method of raising the field electron emitting performance of carbon nanotube film |
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|---|---|---|---|
| CNB01132287XA CN1135588C (en) | 2001-11-23 | 2001-11-23 | Method of raising the field electron emitting performance of carbon nanotube film |
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| CN1349241A CN1349241A (en) | 2002-05-15 |
| CN1135588C true CN1135588C (en) | 2004-01-21 |
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Cited By (1)
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|---|---|---|---|---|
| US10883665B2 (en) | 2015-12-03 | 2021-01-05 | Engineered Controls International, Llc | Low emission nozzles and receptacles |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7341498B2 (en) | 2001-06-14 | 2008-03-11 | Hyperion Catalysis International, Inc. | Method of irradiating field emission cathode having nanotubes |
| CN1301212C (en) * | 2002-09-17 | 2007-02-21 | 清华大学 | Method for adjusting unidimensional nano material direction and shape |
| CN1295731C (en) * | 2002-11-25 | 2007-01-17 | 财团法人工业技术研究院 | Method for implanting metal nano wire or nano tube into field emission source assembly |
| WO2005012162A2 (en) * | 2003-07-09 | 2005-02-10 | Hyperion Catalysis International, Inc. | Field emission devices made with laser and/or plasma treated carbon nanotube mats, films or inks |
| CN100342474C (en) * | 2004-04-21 | 2007-10-10 | 中国科学院上海微系统与信息技术研究所 | Method of ion injecting for increasing emitting performance of carbon mnotube thin film electronic field |
| CN1321223C (en) * | 2006-01-12 | 2007-06-13 | 上海交通大学 | Method for disposing carbon nanometer tube film surface appearance using multiple plasm in order |
| CN101051587B (en) * | 2007-03-22 | 2010-05-19 | 华东师范大学 | Method for improving iron oxide nano line material field transmitting property |
| TW201032259A (en) | 2009-02-20 | 2010-09-01 | Chunghwa Picture Tubes Ltd | Fabricating method of electron-emitting device |
| RU2645153C1 (en) * | 2017-06-07 | 2018-02-16 | Федеральное государственное бюджетное учреждение науки Институт нанотехнологий микроэлектроники Российской академии наук | Method for forming the emitting surface of auto-emission cathodes |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10883665B2 (en) | 2015-12-03 | 2021-01-05 | Engineered Controls International, Llc | Low emission nozzles and receptacles |
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| CN1349241A (en) | 2002-05-15 |
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