CN100416414C - Method for drawing sub-micron ultraviolet luminous pattern on zinc oxide film - Google Patents
Method for drawing sub-micron ultraviolet luminous pattern on zinc oxide film Download PDFInfo
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- CN100416414C CN100416414C CNB2006100495809A CN200610049580A CN100416414C CN 100416414 C CN100416414 C CN 100416414C CN B2006100495809 A CNB2006100495809 A CN B2006100495809A CN 200610049580 A CN200610049580 A CN 200610049580A CN 100416414 C CN100416414 C CN 100416414C
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Abstract
The present invention discloses a method for drawing an ultraviolet luminous pattern of the sub-micron level on a zinc oxide film. The method for drawing an ultraviolet luminous pattern of the sub-micron level on a zinc oxide film comprises the following steps: dissolving zinc acetate dihydrate, trisodium citrate dihydrate and alcohol amine in deionized water solution, and regulating the pH value of the deionized water solution to 10 to 11; then, immersing a clean substrate in the solution, carrying out ultrasonic vibration at 60 DEG C to 90 DEG C, and depositing on the substrate to obtain a zinc oxide film; cleaning the zinc oxide film, removing reaction residues on the surface, and drying the zinc oxide film in an air atmosphere whose temperature is lower than 400 DEG C; placing the zinc oxide film in a scanning electron microscope and irradiating the zinc oxide film by focused electronic beams according to a needed pattern. The method has the advantages of simpleness, low price, convenient operation and easy large-scale preparation. The obtained luminous pattern has high precision and can remain unchanged in air for a long period of time. The present invention can be applied to fields of high-resolution field emission display, high-density information store, etc. In addition, because the luminous pattern can not be visually identified from the appearance, the method can be used for recording secret character information.
Description
Technical field
The present invention relates to draw the luminous characters method of patterning, especially the method for drawing sub-micron ultraviolet luminous pattern on zinc-oxide film.
Background technology
Zinc paste (ZnO) is that a kind of very important II-VI family has direct wide bandgap semiconductor materials, is widely used in fields such as electronics, optoelectronics.Because zinc paste at room temperature has very wide band gap (3.3eV) and very high exciton bind energy (60eV), zinc paste at room temperature has very high ultra-violet light-emitting efficient, is particularly useful for making luminescent devices such as ultraviolet light-emitting diode and ultraviolet laser.In addition, owing to the luminous covering 500-700nm of zinc paste at visible waveband, and adjustable, zinc paste also is widely used in fields such as fluorescent technique and high-resolution Field Emission Display technology.
In field of nanometer technology, on micro-scale to the performance of material carry out the part accurately control and adjusting be a significant challenge, become a big research focus.If we can realize this point, just can on same material, prepare various devices at an easy rate and come with specific function.This just needs this province of material of preparation to have unique optics or electric property.The big dream of in the field of nanometer technology be exactly will be on nanoscale writing and drawing literal and pattern quickly, become possibility thereby make dictionary with up to ten million words be recorded on the material of hand size.Zinc paste, as a kind of luminescent material with superior luminescent properties, if can finding someway, we can accurately control its local luminescent properties, so just might on zinc paste, high precision draw luminous pattern, thereby can be applicable to fields such as high density information storage and high-resolution demonstration.
Summary of the invention
The purpose of this invention is to provide a kind of cheap quick, simple, be easy to extensive on zinc-oxide film the method for drawing sub-micron ultraviolet luminous pattern.
Of the present invention on zinc-oxide film the direct method of drawing sub-micron ultraviolet luminous pattern, employing be the method for electron beam direct irradiation, may further comprise the steps:
1) zinc acetate, sodium citrate and hydramine are dissolved in the deionized water solution, regulate the pH value to 10-11, then clean substrate is immersed in this solution and goes, sonic oscillation under 60 ℃～90 ℃ temperature, react 1-4 hour on substrate deposition obtain zinc-oxide film;
2) clean zinc-oxide film repeatedly with deionized water and ethanol, remove the surface reaction residue, be lower than 400 ℃ of oven dry down;
3) zinc-oxide film is placed scanning electron microscope, shine according to required pattern on zinc-oxide film with focused beam and to draw luminous pattern, the energy of electron beam is 1keV～30keV, and line is 10pA～50nA, beam spot diameter, is 10nm～100nm, and enlargement factor is 50-100000 times.
Above-mentioned hydramine can be triethanolamine or diethanolamine.Said substrate is silicon chip or glass.
Zinc acetate, sodium citrate and hydramine used among the present invention are the commercial goods.The mole dosage ratio of zinc acetate, sodium citrate and hydramine is generally 1～50: 1: 1～20.
The present invention is plotted in the luminous pattern of zinc-oxide film, can adopt the high-resolution cathode-ray fluorescent system that is integrated in the scanning electron microscope to read and record under scan pattern.
The inventive method can change the size and the precision of luminous characters pattern by changing the enlargement factor of scanning electron microscope.Under 5000 times, the live width of the luminous pattern of being drawn can reach 400nm.The luminous pattern of being drawn can remain unchanged in air for a long time, does not still have degeneration after the several months.The inventive method adopts the wet chemistry method to prepare zinc-oxide film under cryogenic conditions, and cheap and simple is easy to mass preparation.Carry out luminous pattern with focused beam and draw, easy operating, the electron beam irradiation can significantly strengthen the ultra-violet light-emitting of this zinc-oxide film, and makes its visible luminous disappearance relevant with defect luminescence.Therefore, the ultra-violet light-emitting through postradiation zone will be better than the not ultra-violet light-emitting of irradiation area greatly, thereby obtains the ultraviolet luminous pattern of submicron order.Compare with the preparation method of patterning of routine, the inventive method is not wanted template and other pre-service, just can form luminous pattern on zinc paste by the electron beam direct irradiation, so unusual simple and fast.Because luminous pattern precision height, this method can be applicable to fields such as high-resolution Field Emission Display and high density information storage.In addition, because luminous pattern can not be discerned from pattern intuitively, this method can be used to write down hieroglyph information.
Description of drawings
Fig. 1 is the stereoscan photograph with the zinc-oxide film of wet chemistry method preparation;
Fig. 2 is the evolution of the cathode-ray fluorescent spectrum of zinc paste under the electron beam irradiation with irradiation time; The illustration in the upper right corner is the variation of the luminous normalization peak value of the ultra-violet light-emitting of zinc paste and visible waveband with the electron beam irradiation time;
Fig. 3 (a) and (b) be respectively scanning electron microscope (SEM) photo and cathode-ray fluorescent (CL) photo that the zinc-oxide film of ultraviolet luminous pattern is arranged in drafting.
Embodiment
Embodiment 1:
With 10ml concentration is the zinc acetate of 0.1M, 2ml concentration is that the sodium citrate of 0.1M and diethanolamine that 10ml concentration is 0.1M are dissolved in the 100ml deionized water, with ammoniacal liquor the pH value of solution is transferred to 10.5, solution temperature is controlled at 70 ℃, clean silicon chip is immersed in the solution, and sonic oscillation in ultrasonic oscillator reacts after 2 hours then, silicon chip is taken out from solution, and deposition obtains zinc-oxide film on silicon chip substrate.
Zinc-oxide film deionized water and ethanol rinsing with obtaining to remove the reaction residue on surface, kept 2 hours drying then in 200 ℃ of air atmospheres.
In field emission scanning electron microscope (Hitachi S4300E/N) zinc-oxide film is observed and the luminous pattern drafting, beam energy is 10keV, and line is 20pA, and beam spot diameter, is about 20nm, and enlargement factor is 5000 times.Shine on zinc-oxide film according to required pattern, postradiation regional zinc oxide luminescent strengthens greatly, obtains ultraviolet luminous pattern.Carry out home position observation and write down luminous pattern with the high-resolution cathode-ray fluorescent system that is integrated in the scanning electron microscope.
Fig. 1 is the field emission scanning electron microscope photo of zinc-oxide film, and as can be seen from the figure film is a polycrystalline structure, and crystal grain is less than 500nm.
Fig. 2 is the evolution of the cathode-ray fluorescent spectrum of zinc paste under electron beam irradiation with irradiation time, and the illustration in the upper right corner is the variation of the luminous normalization peak value of the ultra-violet light-emitting of zinc paste and visible waveband with the electron beam irradiation time.As can be seen from the figure under the irradiation of electron beam, the ultra-violet light-emitting intensity of zinc paste significantly strengthens in 60 seconds.
Fig. 3 (a) and (b) be respectively to write scanning electron microscope (SEM) photo of zinc-oxide film of ultra-violet light-emitting character pattern (ZJU) and monochromatic cathode-ray fluorescent (CL) photo under 385 nanometers.According to the difference of light and shade contrast, from CL photo (Fig. 3 (b)), can clearly find out bright character pattern, but from the shown pattern of SEM photo (Fig. 3 (a)), but can not identify luminous pattern.Under 5000 times, the live width of pattern can reach 400nm.
Claims (3)
1. the method for drawing sub-micron ultraviolet luminous pattern on zinc-oxide film may further comprise the steps:
1) zinc acetate, sodium citrate and hydramine are dissolved in the deionized water solution, regulate the pH value to 9-11, then clean substrate is immersed in this solution and goes, sonic oscillation under 60 ℃～90 ℃ temperature, react 1-4 hour on substrate deposition obtain zinc-oxide film;
2) clean zinc-oxide film repeatedly with deionized water and ethanol, remove the surface reaction residue, be lower than 400 ℃ of oven dry down;
3) zinc-oxide film is placed scanning electron microscope, shine according to required pattern on zinc-oxide film with focused beam and to draw luminous pattern, the energy of electron beam is 1keV～30keV, and line is 10pA～50nA, beam spot diameter, is 10nm～100nm, and enlargement factor is 50-100000 times.
2. according to claim 1 on zinc-oxide film the method for drawing sub-micron ultraviolet luminous pattern, it is characterized in that said hydramine is triethanolamine or diethanolamine.
3. according to claim 1 on zinc-oxide film the method for drawing sub-micron ultraviolet luminous pattern, it is characterized in that said substrate is silicon chip or glass.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100495809A CN100416414C (en) | 2006-02-24 | 2006-02-24 | Method for drawing sub-micron ultraviolet luminous pattern on zinc oxide film |
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| Application Number | Priority Date | Filing Date | Title |
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| CNB2006100495809A CN100416414C (en) | 2006-02-24 | 2006-02-24 | Method for drawing sub-micron ultraviolet luminous pattern on zinc oxide film |
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| CN1837965A CN1837965A (en) | 2006-09-27 |
| CN100416414C true CN100416414C (en) | 2008-09-03 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102219557B (en) * | 2011-04-15 | 2012-10-24 | 河南大学 | Preparation method of patterned zinc oxide film |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000243991A (en) * | 1999-02-19 | 2000-09-08 | Canon Inc | Method of forming zinc oxide film and semiconductor element using same |
| JP2004013042A (en) * | 2002-06-11 | 2004-01-15 | Sharp Corp | Method for forming thin film pattern |
| JP2004149367A (en) * | 2002-10-31 | 2004-05-27 | Japan Science & Technology Agency | Aqueous solution for producing zinc oxide particle or film, and method for producing zinc oxide particle or film |
| CN1613774A (en) * | 2004-11-16 | 2005-05-11 | 浙江大学 | Preparation for zinc oxide nanometer material |
| US20050250052A1 (en) * | 2004-05-10 | 2005-11-10 | Nguyen Khe C | Maskless lithography using UV absorbing nano particle |
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- 2006-02-24 CN CNB2006100495809A patent/CN100416414C/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000243991A (en) * | 1999-02-19 | 2000-09-08 | Canon Inc | Method of forming zinc oxide film and semiconductor element using same |
| JP2004013042A (en) * | 2002-06-11 | 2004-01-15 | Sharp Corp | Method for forming thin film pattern |
| JP2004149367A (en) * | 2002-10-31 | 2004-05-27 | Japan Science & Technology Agency | Aqueous solution for producing zinc oxide particle or film, and method for producing zinc oxide particle or film |
| US20050250052A1 (en) * | 2004-05-10 | 2005-11-10 | Nguyen Khe C | Maskless lithography using UV absorbing nano particle |
| CN1613774A (en) * | 2004-11-16 | 2005-05-11 | 浙江大学 | Preparation for zinc oxide nanometer material |
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