CN1130263A - Method for making quantum line ultra-fine figure - Google Patents
Method for making quantum line ultra-fine figure Download PDFInfo
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- CN1130263A CN1130263A CN 95100463 CN95100463A CN1130263A CN 1130263 A CN1130263 A CN 1130263A CN 95100463 CN95100463 CN 95100463 CN 95100463 A CN95100463 A CN 95100463A CN 1130263 A CN1130263 A CN 1130263A
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- raster
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- 238000000034 method Methods 0.000 title claims abstract description 42
- 229910052751 metal Inorganic materials 0.000 claims abstract description 26
- 239000002184 metal Substances 0.000 claims abstract description 26
- 238000005530 etching Methods 0.000 claims abstract description 23
- 239000000463 material Substances 0.000 claims abstract description 21
- 239000000758 substrate Substances 0.000 claims abstract description 19
- 238000001259 photo etching Methods 0.000 claims abstract description 14
- 238000002834 transmittance Methods 0.000 claims description 8
- 238000005516 engineering process Methods 0.000 claims description 7
- 239000011248 coating agent Substances 0.000 claims description 6
- 238000000576 coating method Methods 0.000 claims description 6
- 239000004065 semiconductor Substances 0.000 claims description 6
- 239000012528 membrane Substances 0.000 claims description 5
- 238000001020 plasma etching Methods 0.000 claims description 4
- 230000007704 transition Effects 0.000 claims description 4
- 230000005540 biological transmission Effects 0.000 claims description 3
- 238000001312 dry etching Methods 0.000 claims description 2
- 230000008020 evaporation Effects 0.000 claims description 2
- 238000001704 evaporation Methods 0.000 claims description 2
- 238000009738 saturating Methods 0.000 claims description 2
- 239000012780 transparent material Substances 0.000 claims description 2
- 238000001459 lithography Methods 0.000 claims 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 13
- 239000004926 polymethyl methacrylate Substances 0.000 description 13
- 239000004642 Polyimide Substances 0.000 description 10
- 229920002120 photoresistant polymer Polymers 0.000 description 10
- 229920001721 polyimide Polymers 0.000 description 10
- 238000010884 ion-beam technique Methods 0.000 description 9
- 230000005469 synchrotron radiation Effects 0.000 description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 239000002096 quantum dot Substances 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229910052581 Si3N4 Inorganic materials 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 241000218202 Coptis Species 0.000 description 1
- 235000002991 Coptis groenlandica Nutrition 0.000 description 1
- 238000001015 X-ray lithography Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000000609 electron-beam lithography Methods 0.000 description 1
- 238000000407 epitaxy Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000007737 ion beam deposition Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 230000002459 sustained effect Effects 0.000 description 1
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- Diffracting Gratings Or Hologram Optical Elements (AREA)
- Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)
Abstract
The invented method consists of using the steep side wall X raster to make the initial raster photoetching mask pattern, after it is converted into etched mask pattern, then converted again on the needed substrate. The characteristic lies in that in the course of the initial raster pattern converting to the etching mask, the pattern is firstly converted on the thin layer of supporting material to form into supporting raster, then the metal thin layer is coated on the surface of the raster to obtain the quantum line photoetching mask formed of quantum metal lines attached to the vertical sidewall of the supporting raster, removing the supporting raster, the etching mask pattern is finished. Said method has the advantages of simple process, large making area, and not limitted by the resolution of the material.
Description
The present invention relates to the quantum line ultra-fine figure method for making.
Quantum line and quantum dot are the low-dimensional quantum structures that a class has obvious quantum effect, and its live width is generally below 500 dusts, and make the superfine graph with quantum size precision is very difficult on technology." semiconductor quantum microstructure and progress thereof " (" the Nature exploration " 1993.3) literary composition is described respectively special construction growth method and the graphic printing technical method that has occurred in the prior art, and having introduced another kind of method on the Japanese photon factory annual report (1991) is phase shifting method.Described special construction growth method is on the substrate of certain figure, utilizes epitaxy technology grown quantum line, and this method has the advantage that is not subjected to the graphics resolution restriction, but its initial quantum size figure is difficult to obtain.Described graphic printing technology is to utilize electron beam lithography to form the quantum microstructure graph, owing to use electron beam exposure, not only the time shutter is oversize, exposure area is little, and the sharpness of figure is subjected to the restriction of resist layer resolution, cost of equipment is also very expensive, and it can not be produced in enormous quantities.Phase shifting method is to utilize light wave when seeing through the material of two adjacent different-thickness, form the characteristic of 180 ° of phase differential at the surface of contact place, prepare hyperfine structure, but this method needs the extremely thickness of strict control of material, this is very inconvenient and more inaccessible when technological operation.
Purpose of the present invention is just in order to overcome above deficiency, provides easily to implement on a kind of technology, and the method that can make the larger area superfine graph.
Purpose of the present invention is realized by following mode.
The method for making of quantum superfine graph of the present invention comprises:
1. make steep sidewall x transmittance grating as initial grid photo-etching mask, the steep sidewall x transmittance grating that for example utilizes laser hologram and ion beam etching and synchrotron radiation optical graving to get;
2. the raster graphic on the initial raster mask is converted to the etching mask figure;
3. the quantum superfine graph on the etching mask is transformed on the semiconductor chip, it is characterized in that, the step that the raster graphic on the initial raster mask is converted to the etching mask figure is:
(1) on substrate, is coated with the propping material thin layer;
(2) utilize x light photoetching method that the raster graphic on the initial mask is transformed on the propping material thin layer, be the support grating;
(3) supporting upward even metal-coated membrane thin layer of grating surface (containing the surface, two side);
(4) metal film on the reservation two side removes the remainder metallic diaphragm quarter with the dry etching method, promptly obtains supporting the quantum line mask graph that the thin metal layer on the grating two side constitutes by being attached to;
(5) remove propping material, promptly obtain quantum line ultra-fine figure.
Make in the process of initial mask at the above, employed steep sidewall x transmittance grating is meant that angle between this grating sidewall and the substrate surface normal is less than 5 ° x transmittance grating, the x transmittance grating that produces by laser hologram and ion beam etching and synchrotron radiation x light photoetching method for example, its raster density is selected according to the density of required figure, for example every millimeter 1000 line.
Raster graphic on the initial raster mask is being converted in the process of etching mask figure, the described propping material that on substrate, is coated with, comprise generally speaking and be coated with supporting layer and transition bed, employed support layer material is the transparent material of x ray, for example: polyimide (PI) or silit (SiC) or silicon nitride (SiN) etc., described buffer layer material is an x ray resist, as photoresist (PMMA or PBS), at first raster graphic is transformed on the transition bed, and then be transformed on the supporting layer, form to support grating, describedly supporting metal-coated membrane thin layer on the grating surface, be meant under vacuum state, come the plating rete with the method for sputter or evaporation, its thickness of coating is the width of fine rule in the required superfine graph, usually below 500 dusts, employed metal is meant the not metal material of saturating x light, for example gold, platinum etc.
In the process of actual fabrication quantum ultra micro fine rule etching mask figure, also can directly use required substrate, for example semiconductor material as substrate, only need be coated with x ray resist as layer of support material, as photoresist PMMA, PBS etc. at this moment on substrate.Directly raster graphic is transformed on the photoresist layer then, grating promptly is supported, carry out the operation of applying metal thin layer operation again, employed metal is the metal of anti-reactive ion etching, for example gold, platinum, chromium, nickel etc., obtain the quantum line mask after, remove and support grating and obtain etching mask, this way has been saved the operation that is coated with transition bed, and operating process is simplified.
Compared with prior art, the present invention utilizes the steep sidewall x transmittance grating of suitable line density as initial mask, utilize the synchrotron radiation photoetching figure to be transformed on the propping material of substrate surface, plating has the method for quantum size thickness metal film on its two side, obtain the quantum line mask of superfine graph, this mask figure good stability, can reuse, help obtaining quantum line figure clearly, owing to be to support grating two side plated film, make the density multiplication of quantum line figure simultaneously.Method for making of the present invention is not subjected to the restriction of material discrimination rate, and area big (centimetre magnitude), and technology is comparatively simple.Can make multiple hyperfine structure figure, as quantum dot, quantum box etc.
Be further described below in conjunction with embodiment and accompanying drawing:
Embodiment 1. makes the initial raster mask
(1) be substrate slice with the smooth glass of cleaning, utilize whirl coating to be coated with the polyimide coating that a layer thickness is about 2 microns equably, the 300c baking is 2 hours in the far infrared baking oven
(2) utilize ion beam deposition to plate thick about 0.6 micron golden film in the polyimide coating surface
(3) coat thick 0.5 micron AZ-1350 photoresist equably on golden film, 90 ℃ were dried by the fire 25 minutes in the far infrared baking oven
(4) in argon laser (wavelength is 457.9nm) holographic light path, expose, just on the AZ-1350 photoresist, formed raster graphic after the development.Grid stroke density is every millimeter 1000 line, and exposure is about 200 millijoules/cm
2, about 1 minute of development time, developer solution are 0.6% NaOH aqueous solution, development temperature is 20-25 ℃
(5) substrate of carrying out raster graphic is placed on etching in the ion beam etching machine, just the photoresist grating figure has been transformed on the golden film.Etching condition is: ion energy 500 electron volts, 0.6 milliampere/cm of ion beam current density
2, about 10 minutes of etching time
(6) be stained with sizeable copper ring as supporting in the one side that figure is arranged with epoxy resin at last, erode glass substrate with hydrofluorite again, obtain the golden transmission grating figure that supports by transparent polyimide
(7) repeat the technology of above-mentioned (1) and (2)
(8) coat thick about 1.0 microns PMMA photoresist equably on golden film, the 130C baking is 30 minutes in the far infrared baking oven
(9) golden transmission grating figure is transformed on the PMMA with x light exposure device at x light photoetching station, Hefei National synchrotron radiation laboratory, exposure wavelength 0.5-0.2nm, exposure 3000 milliamperes minutes, vacuum tightness is 3.0*10-6Pa, wet development, developer solution is 4-methyl-pentanone-2: isopropyl alcohol=3: 1, about 25 seconds of development time
(10) repeat (5) and (6), just obtained the steep synchrotron radiation x photoetching grating mask of grating sidewall, i.e. the initial raster mask
Embodiment 2. makes the x X-ray lithography X mask of quantum superfine graph.
(1) utilizing lacquering technique evenly to be coated with a bed thickness on the glass sheet of smooth cleaning is 2 microns polyimide coating (propping material), be placed in the far infrared baking oven 300 ℃ of bakings two hours, and then evenly to be coated with thick thereon be 0.25 micron PMMA photoresist film, 25 ℃ of room temperatures, humidity is less than 50%, and 130 ℃ were dried by the fire 30 minutes in the far infrared baking oven;
(2) utilize x light exposure device that initial photoetching mask graph is transferred on the PMMA layer at x light photoetching station, Hefei National synchrotron radiation laboratory, exposure and development conditions are with 1. (9);
(3) utilize the ion beam etching machine that the PMMA grating is transferred on the polyimide layer, obtain polyimide and support grating;
(4) utilize the ion beam etching machine, gold-plated on support grating all surface, the two side thickness is respectively 50nm and 100nm;
(5) in the ion beam etching machine, vertically etch away the golden film that supports on grating surface and the bottom land, promptly obtain the quantum line mask graph that constitutes by the sidewall golden membranous layer;
(6) sticking support ring, and in hydrofluoric acid solution, erode glass substrate, promptly getting quantum line x mask, mask size is 0.8cm
Embodiment 3. is a substrate with required silicon chip, makes the reactive ion etching mask of quantum line ultra-fine figure
(1) utilizing lacquering technique evenly to be coated with thick on the silicon chip of smooth cleaning is 0.25 micron PMMA photoresist, and 25 ℃ of room temperatures, humidity be less than 50%, is placed in the far infrared baking oven 130 ℃ of bakings 30 minutes;
(2) utilize x light exposure device that initial photoetching mask graph is transformed on the PMMA at x light photoetching station, Hefei National synchrotron radiation laboratory, exposure and development conditions are with 1. (9)
(3) utilize the ion beam etching machine gold-plated at PMMA grating all surface.Two side thickness are respectively 50nm and 100nm;
(4) in the ion beam etching machine, vertically etch away golden film on PMMA grating surface and the bottom land, promptly obtain the quantum line mask graph that constitutes by the sidewall golden membranous layer;
(5) remove the PMMA grating with the plasma oxidation method, the condition of removing photoresist is: vacuum tightness 6.7Pa, and the about 75v of voltage, the time is about 1 hour, after the PMMA grating has gone, stays the superfine graph of gold on silicon chip, is the reactive ion etching mask, and mask size is 0.8cm.
On the silicon chip that quantum line is arranged, repeat the overall process of embodiment 2, the grating orientation on the initial raster mask is placed with existing quantum line is vertical, then obtain being vertically intersected on quantum dot figure a little at last.
Below provide the synoptic diagram in the operational sequence
Fig. 1 is the structural representation with initial raster mask of cliff.(1) sufficient polyimide rete among the figure; (2) be the copper sustained ring, (3) cliff grating gold thread.
Fig. 2 is the structural representation of quantum line mask.Quantum metal wire (4) is attached on two sidewalls that support grating (5) among the figure, and a grid grating is made of transparent polyimide.
Claims (10)
1. the method for making of a quantum line ultra-fine figure comprises 1) the initial grid photo-etching mask of the steep sidewall x transmittance grating of making; 2) raster graphic on the initial raster is converted to figure on the quantum line etching mask; 3) figure on the quantum line etching mask is transformed on the semiconductor chip, it is characterized in that, the step that the figure on the grid photo-etching mask is converted to the etching mask figure is:
1) on substrate, is coated with the propping material thin layer;
2) utilize the X smooth lithography technology that the initial raster mask graph is transformed on the above-mentioned propping material thin layer, promptly support grating;
3) supporting upward even metal-coated membrane thin layer of grating surface (containing the surface, two side);
4) metal film on the reservation two side removes the remainder metallic diaphragm quarter with the dry etching method, promptly obtains supporting the quantum line mask that the coat of metal on the grating two side constitutes by being attached to;
5) remove the support grating, promptly obtain etching mask.
2. method for making as claimed in claim 1 is characterized in that described steep sidewall x transmittance grating is meant that angle between grating sidewall and the substrate surface normal is less than 5 ° X-ray transmission grating.
3. method for making as claimed in claim 1 is characterized in that described propping material comprises supporting layer and transition bed, and wherein support layer material is an x ray transparent material, and buffer layer material is an x ray resist.
4. method for making as claimed in claim 1 is characterized in that even metal-coated membrane thin layer is meant under vacuum state on the support grating surface, with the method applying metal thin layer of sputter or evaporation.
5. method for making as claimed in claim 1 is characterized in that the thickness of described applying metal thin layer equals the width of fine rule in the required superfine graph.
6. method for making as claimed in claim 1, used metal is meant the not metal of saturating x light when it is characterized in that described applying metal thin layer.
7. method for making as claimed in claim 1 is characterized in that described transparent substrates can be replaced by semiconductor chip.
8. as claim 1 or 7 described method for makings, it is characterized in that described propping material coating on semiconductor chip is an x ray resist.
9. as claim 1 or 7 or 8 described method for makings, it is characterized in that described to be meant the metal of anti-reactive ion etching in the metal-coated membrane thin layer on the support grating of x ray resist work with metal.
10. the quantum line mask of using in the method for making as claimed in claim 1, include transparent substrates and quantum metal line pattern, it is characterized in that described substrate is provided with the support raster graphic of steep sidewall, described quantum metal line pattern is attached on two sidewalls that support grating.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 95100463 CN1063552C (en) | 1995-02-28 | 1995-02-28 | Method for making quantum line ultra-fine figure |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 95100463 CN1063552C (en) | 1995-02-28 | 1995-02-28 | Method for making quantum line ultra-fine figure |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1130263A true CN1130263A (en) | 1996-09-04 |
| CN1063552C CN1063552C (en) | 2001-03-21 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 95100463 Expired - Fee Related CN1063552C (en) | 1995-02-28 | 1995-02-28 | Method for making quantum line ultra-fine figure |
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| Country | Link |
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| CN (1) | CN1063552C (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100419789C (en) * | 2002-11-22 | 2008-09-17 | Ovd基尼格拉姆股份公司 | Thin layer configuration with diffractive optical structures producing lens-like effects |
| CN110246762A (en) * | 2019-06-12 | 2019-09-17 | 中国科学院上海微系统与信息技术研究所 | The preparation method and device architecture of metal sidewall |
-
1995
- 1995-02-28 CN CN 95100463 patent/CN1063552C/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100419789C (en) * | 2002-11-22 | 2008-09-17 | Ovd基尼格拉姆股份公司 | Thin layer configuration with diffractive optical structures producing lens-like effects |
| CN110246762A (en) * | 2019-06-12 | 2019-09-17 | 中国科学院上海微系统与信息技术研究所 | The preparation method and device architecture of metal sidewall |
| CN110246762B (en) * | 2019-06-12 | 2021-04-02 | 中国科学院上海微系统与信息技术研究所 | Preparation method and device structure of metal sidewall |
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| Publication number | Publication date |
|---|---|
| CN1063552C (en) | 2001-03-21 |
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