CN102243967B - Preparation method for cathode of ballistic field-emitting display device based on porous dielectric material thin film - Google Patents
Preparation method for cathode of ballistic field-emitting display device based on porous dielectric material thin film Download PDFInfo
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- CN102243967B CN102243967B CN 201110136861 CN201110136861A CN102243967B CN 102243967 B CN102243967 B CN 102243967B CN 201110136861 CN201110136861 CN 201110136861 CN 201110136861 A CN201110136861 A CN 201110136861A CN 102243967 B CN102243967 B CN 102243967B
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- 239000003989 dielectric material Substances 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000010409 thin film Substances 0.000 title abstract description 5
- 238000000034 method Methods 0.000 claims abstract description 15
- 244000025254 Cannabis sativa Species 0.000 claims description 21
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 21
- 235000013870 dimethyl polysiloxane Nutrition 0.000 claims description 21
- CXQXSVUQTKDNFP-UHFFFAOYSA-N octamethyltrisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)O[Si](C)(C)C CXQXSVUQTKDNFP-UHFFFAOYSA-N 0.000 claims description 21
- 238000004987 plasma desorption mass spectroscopy Methods 0.000 claims description 21
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 21
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 20
- 229910052710 silicon Inorganic materials 0.000 claims description 20
- 239000010703 silicon Substances 0.000 claims description 20
- 229910052751 metal Inorganic materials 0.000 claims description 17
- 239000002184 metal Substances 0.000 claims description 17
- 238000004544 sputter deposition Methods 0.000 claims description 9
- 238000005516 engineering process Methods 0.000 claims description 8
- 239000000758 substrate Substances 0.000 claims description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 230000007797 corrosion Effects 0.000 claims description 6
- 238000005260 corrosion Methods 0.000 claims description 6
- 238000001312 dry etching Methods 0.000 claims description 6
- 238000005530 etching Methods 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- 229910052737 gold Inorganic materials 0.000 claims description 5
- 238000000151 deposition Methods 0.000 claims description 4
- 230000008021 deposition Effects 0.000 claims description 4
- 229910052763 palladium Inorganic materials 0.000 claims description 4
- 229910052709 silver Inorganic materials 0.000 claims description 4
- 241000196324 Embryophyta Species 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 238000009413 insulation Methods 0.000 claims description 3
- 239000012212 insulator Substances 0.000 claims description 3
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 3
- 239000012528 membrane Substances 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 238000002161 passivation Methods 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 3
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- 238000004519 manufacturing process Methods 0.000 description 4
- 229910021426 porous silicon Inorganic materials 0.000 description 4
- 239000002159 nanocrystal Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000002048 anodisation reaction Methods 0.000 description 1
- 238000007743 anodising Methods 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
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- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
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Abstract
The invention relates to a preparation method for a cathode of a ballistic field-emitting display device based on a porous dielectric material thin film. The field-emitting cathode consists of an upper emitting electrode, a middle porous dielectric material thin film and a lower emitting electrode, wherein the porous dielectric material thin film is prepared by chemical synthesis and a physical method. The device in the invention has a simple structure, low driving voltage and electron emitting rate of over 5 percent; meanwhile, during preparation, the preparation method has the advantages that: the preparation process is simple, the material is not needed to be treated specially, the emitting cathode is not needed to be activated specially and electron emission can be performed by directly applying the driving voltage. By adoption of the process, the preparation cost is much lower than that of the prior art; and the preparation method is suitable for large-scale production.
Description
Technical field
The invention belongs to vacuum electronic emission type technical field of flat panel display, particularly a kind of preparation method of the trajectory field emission display negative electrode based on the porous dielectric material film.
Background technology
In fact the ballistic electron emission refers to utilize a kind of accurate ballistic electron that porous silicon is realized to launch, and result the earliest is the nineteen ninety-five report.This emission has higher efficient and little fluctuating, is considered to overcome many shortcomings of Spindt type negative electrode.1999, develop in Matsushita Electric Industrial Co based on the device example that is called as ballistic electron surface emitting demonstration (Ballistic electron Surface-emitting Display is called for short BSD) of this negative electrode.
Originally the BSD negative electrode is made on silicon chip, develops on deposited polycrystalline silicon thin film on substrate of glass afterwards and makes.At first prepare column electrode with method of diffusion being oriented on the N-shaped silicon chip of 100.Then with the liquid phase CVD method deposition 1.5 thick un-doped polysilicons of μ m.Then at the HF(50% of 1:1) and ethanolic solution in carry out the processing of 12s anodization porous, current density is 30mA/cm
2, the tungsten lamp with 500W shines on the distance of 20cm simultaneously.After carrying out the 60min oxidation processes under 900 ℃, the golden film that deposits 15nm is as grid to porous silicon.Grid figure newly forms with the ion grinding technique.In order to reduce resistance, with thicker aluminium film production bus electrode.
The emission threshold threshold voltage of BSD negative electrode is approximately 8V, and when grid voltage reached 30V, emission reached 2mA/cm
2, can satisfy the demand that high brightness shows.If the ratio of emission current and grid current is defined as emissivity, when grid voltage was between 22 ~ 30V, emissivity reached 1%.This negative electrode of real surface can still can work during up to 10Pa at pressure.
The loose structure that forms in anodizing process is actually by nano particle and forms, and the Quick Oxidation process makes nanocrystal and on every side polycrysalline silcon surface form layer of silicon dioxide.Due to heat emission, electronics enters porous silicon from substrate.Collision probability between electronics and nanocrystal is little, has caused the mean free path of electronics in nanocrystal to be far longer than free path in the body silicon materials, therefore is considered to accurate ballistic electron.Due to the existence of oxide layer, be able to apply highfield (10 in porous silicon layer
7V/m).Under this highfield, electronics moves to grid, and obtains the energy of several electron-volts, and is transmitted in vacuum by the gold layer.
BSD has lot of advantages, and is as little in beam divergence angle, and self-focusing function, antipollution and can be than working under low vacuum etc. be arranged.
The topmost shortcoming of BSD is that emission effciency is low.
Summary of the invention
the objective of the invention is for overcoming the deficiencies in the prior art part, a kind of device electronics operation zero collision that has is proposed, the electron focusing ability is strong, emission effciency is high, device architecture is simple, driving voltage is low, the advantages such as low cost of manufacture, possesses simultaneously preparation technology simple, material need not special processing, emitting cathode does not need special activation to process yet, directly apply driving voltage and just can produce the advantage of electron emission, device cost is significantly less than oneself technology, the preparation method based on the trajectory field emission display negative electrode of porous dielectric material film who is fit to large-scale production.
For achieving the above object, the technical solution used in the present invention is:
1) at first prepare by dark dry etching the densely covered silicon nanometer grass array that diameter is 10 ~ 200nm on the Si substrate;
2) then obtain diameter as the dielectric material film of the densely covered nanohole array of 10 ~ 200nm take silicon nanometer grass array as template by mould rotating technology;
3) each deposit thickness of positive and negative at the dielectric material film that is densely covered with nanohole array is the metal electrode of tens nanometers and hundreds of nanometer;
4) adopt silk screen print method to print row-column electrode on the metal electrode of the positive and negative of dielectric material film, and print insulator separation with silk screen print method on the crosspoint of row-column electrode.
The etching gas of the dark dry etching of described step 1) is SF6, and flow is 100sccm, and passivation gas is C4F8, flow is 100sccm, etching power 700W, etch period 21min, nanometer natural plant height degree is 10 μ m, and nanometer grass diameter is 10 ~ 200nm, and nanometer grass spacing is 10 ~ 200nm.
Described step 2) PDMS and curing agent thereof are made into colloidal solution by the mass ratio of 10:1, and colloidal solution is dropped on the Si substrate of the silicon nanometer grass array that gathers, be placed in the closed container that vacuum degree is 10-1Pa and remove the bubble in PDMS solution and to make PDMS solution fully fill gap between silicon nanometer grass, at last its insulation was solidified 24 hours at 100 ℃, to make the PDMS thickness after levelling be 100nm by controlling the PDMS titer; PDMS after solidifying again was immersed in the KOH solution of 90 ℃ corrosion 3 hours together with silicon chip, silicon chip and the corrosion of nanometer grass thereof is clean, and the sample after corroding with deionized water ultrasonic cleaning 10min after nitrogen dry up, obtaining thickness is that 10-200nm, aperture are that 10 ~ 200nm, pitch of holes are the PDMS porous membrane of 10 ~ 200nm.
Described step 3) adopts magnetron sputtering deposition to prepare the upper strata metal electrode at the positive and negative of the dielectric material film that is densely covered with nanohole array, the lower metal electrode, sputtering power is 500W, argon flow amount is 20sccm, the sputtering time of upper strata metal electrode is 1min, film thickness is 25nm, and the sputtering time of lower metal electrode is 10min, and corresponding film thickness is 250nm.
Described metal electrode adopts Pt, Pd, Au, Ag or the Cu that work function is low and physical and chemical performance is stable.
Device architecture of the present invention is simple, and driving voltage is low, and electron emissivity surpasses 5%; Simultaneously, possess preparation technology for the manufacturing of this device simple, material need not special processing, and emitting cathode does not need special activation to process, and just can produce the advantage of electron emission by directly applying driving voltage; Adopting the manufacturing cost of this technique to be significantly less than oneself has technology, and suitable large-scale production.
Description of drawings
The present invention is described in further detail below in conjunction with the drawings and specific embodiments.
Fig. 1-Fig. 4 is preparation flow figure of the present invention, and wherein, the figure in every picture group (b) is the A-A cutaway view of figure (a).
Embodiment
Below in conjunction with accompanying drawing, the present invention is described in further detail.
1) referring to Fig. 1, at first prepare by dark dry etching the densely covered silicon nanometer grass array that diameter is 10 ~ 200nm on the Si substrate;
Wherein the etching gas of dark dry etching is SF6, and flow is 100sccm, and passivation gas is C4F8, flow is 100sccm, etching power 700W, etch period 21min, nanometer natural plant height degree is 10 μ m, and nanometer grass diameter is 10 ~ 200nm, and nanometer grass spacing is 10 ~ 200nm.
2) then obtain diameter as the dielectric material film of the densely covered nanohole array of 10 ~ 200nm take silicon nanometer grass array as template by mould rotating technology;
Its concrete preparation process is as follows:
Referring to Fig. 2, PDMS and curing agent thereof are made into colloidal solution by the mass ratio of 10:1, and colloidal solution is dropped on the Si substrate of the silicon nanometer grass array that gathers, be placed in the closed container that vacuum degree is 10-1Pa and remove the bubble in PDMS solution and to make PDMS solution fully fill gap between silicon nanometer grass, at last its insulation was solidified 24 hours at 100 ℃, to make the PDMS thickness after levelling be 100nm by controlling the PDMS titer; Referring to Fig. 3, PDMS after solidifying again was immersed in the KOH solution of 90 ℃ corrosion 3 hours together with silicon chip, silicon chip and the corrosion of nanometer grass thereof is clean, and the sample after corroding with deionized water ultrasonic cleaning 10min after nitrogen dry up, obtaining thickness is that 10-200nm, aperture are that 10 ~ 200nm, pitch of holes are the PDMS porous membrane of 10 ~ 200nm.
3) positive and negative at the dielectric material film that is densely covered with nanohole array adopts magnetron sputtering deposition to prepare upper strata Pt, Pd, Au, Ag or Cu electrode, the Pt of lower floor, Pd, Au, Ag or Cu electrode, sputtering power is 500W, argon flow amount is 20sccm, the sputtering time of upper strata metal electrode is 1min, film thickness is 25nm, and the sputtering time of lower metal electrode is 10min, and corresponding film thickness is 250nm.
4) adopt silk screen print method to print row-column electrode on the metal electrode of the positive and negative of dielectric material film, and print insulator separation with silk screen print method on the crosspoint of row-column electrode.
Although below by reference to the accompanying drawings embodiment of the present invention are described, the present invention is not limited to above-mentioned specific embodiments, and above-mentioned specific embodiments is only schematic, guiding, rather than restrictive.Those of ordinary skill in the art in the situation that do not break away from the scope that claim of the present invention is protected, can also make a variety of forms under the enlightenment of this specification, these all belong to the row of the present invention's protection.
Claims (5)
1. based on the preparation method of the trajectory field emission display negative electrode of porous dielectric material film, it is characterized in that:
1) at first prepare by dark dry etching the densely covered silicon nanometer grass array that diameter is 10 ~ 200nm on the Si substrate;
2) then obtain diameter as the dielectric material film of the densely covered nanohole array of 10 ~ 200nm take silicon nanometer grass array as template by mould rotating technology;
3) each deposit thickness of positive and negative at the dielectric material film that is densely covered with nanohole array is the metal electrode of tens nanometers and hundreds of nanometer;
4) adopt silk screen print method to print row-column electrode on the metal electrode of the positive and negative of dielectric material film, and print insulator separation with silk screen print method on the crosspoint of row-column electrode.
2. the preparation method of the trajectory field emission display negative electrode based on the porous dielectric material film according to claim 1, it is characterized in that: the etching gas of the dark dry etching of described step 1) is SF6, flow is 100sccm, passivation gas is C4F8, and flow is 100sccm, etching power 700W, etch period 21min, nanometer natural plant height degree is 10 μ m, and nanometer grass diameter is 10 ~ 200nm, and nanometer grass spacing is 10 ~ 200nm.
3. the preparation method of the trajectory field emission display negative electrode based on the porous dielectric material film according to claim 1, it is characterized in that: described step 2) PDMS and curing agent thereof are made into colloidal solution by the mass ratio of 10:1, and colloidal solution is dropped on the Si substrate of the silicon nanometer grass array that gathers, be placed in the closed container that vacuum degree is 10-1Pa and remove the bubble in PDMS solution and to make PDMS solution fully fill gap between silicon nanometer grass, at last its insulation was solidified 24 hours at 100 ℃, to make the PDMS thickness after levelling be 100nm by controlling the PDMS titer, PDMS after solidifying again was immersed in the KOH solution of 90 ℃ corrosion 3 hours together with silicon chip, silicon chip and the corrosion of nanometer grass thereof is clean, and the sample after corroding with deionized water ultrasonic cleaning 10min after nitrogen dry up, obtaining thickness is that 10-200nm, aperture are that 10 ~ 200nm, pitch of holes are the PDMS porous membrane of 10 ~ 200nm.
4. the preparation method of the trajectory field emission display negative electrode based on the porous dielectric material film according to claim 1, it is characterized in that: described step 3) adopts magnetron sputtering deposition to prepare the upper strata metal electrode at the positive and negative of the dielectric material film that is densely covered with nanohole array, the lower metal electrode, sputtering power is 500W, argon flow amount is 20sccm, the sputtering time of upper strata metal electrode is 1min, film thickness is 25nm, the sputtering time of lower metal electrode is 10min, and corresponding film thickness is 250nm.
5. the preparation method of according to claim 1 or 4 described trajectory field emission display negative electrodes based on the porous dielectric material film, it is characterized in that: described metal electrode adopts Pt, Pd, Au, Ag or the Cu that work function is low and physical and chemical performance is stable.
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CN110504327B (en) * | 2018-05-17 | 2020-12-22 | 中国科学院苏州纳米技术与纳米仿生研究所 | Ballistic transport Schottky diode based on nano array and manufacturing method thereof |
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