CN100466171C - High depth-width ratio deep sub-micrometer, nanometer metal structure making process based on self-supporting thin film - Google Patents
High depth-width ratio deep sub-micrometer, nanometer metal structure making process based on self-supporting thin film Download PDFInfo
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- CN100466171C CN100466171C CNB2004101018738A CN200410101873A CN100466171C CN 100466171 C CN100466171 C CN 100466171C CN B2004101018738 A CNB2004101018738 A CN B2004101018738A CN 200410101873 A CN200410101873 A CN 200410101873A CN 100466171 C CN100466171 C CN 100466171C
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 87
- 239000002184 metal Substances 0.000 title claims abstract description 87
- 238000000034 method Methods 0.000 title claims description 36
- 239000010409 thin film Substances 0.000 title 1
- 229910052737 gold Inorganic materials 0.000 claims abstract description 27
- 238000010894 electron beam technology Methods 0.000 claims abstract description 21
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 17
- 239000007788 liquid Substances 0.000 claims abstract description 16
- 238000009713 electroplating Methods 0.000 claims abstract description 14
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 26
- 239000010931 gold Substances 0.000 claims description 26
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 24
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 18
- 239000011651 chromium Substances 0.000 claims description 16
- 239000000853 adhesive Substances 0.000 claims description 13
- 230000001070 adhesive effect Effects 0.000 claims description 13
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 238000007747 plating Methods 0.000 claims description 8
- 238000000609 electron-beam lithography Methods 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 229920002120 photoresistant polymer Polymers 0.000 claims description 5
- 238000013459 approach Methods 0.000 claims description 4
- 238000005566 electron beam evaporation Methods 0.000 claims description 4
- 238000005530 etching Methods 0.000 claims description 3
- 238000010884 ion-beam technique Methods 0.000 claims description 3
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract 2
- 238000000151 deposition Methods 0.000 abstract 1
- 239000003292 glue Substances 0.000 abstract 1
- 238000011031 large-scale manufacturing process Methods 0.000 abstract 1
- 239000000693 micelle Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 5
- 229910052581 Si3N4 Inorganic materials 0.000 description 3
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
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- Electroplating Methods And Accessories (AREA)
- Exposure Of Semiconductors, Excluding Electron Or Ion Beam Exposure (AREA)
- Preparing Plates And Mask In Photomechanical Process (AREA)
- Micromachines (AREA)
Abstract
The invention bases on metal structure manufacture technology of deep sub-micron and nanometer for high aspect ratio of self-support film comprises: 1. depositing thin Cr and Au on front face of self-support film; 2. whirling electron micelle on thin Cr/Au surface to exposure and develop the electron beam; 3. putting the slice into electroplate liquid to electroplate metal firstly; 4. whirling X-ray resist on front face of slice; 5. taking X-ray exposure and develop from the film back surface; 6. electroplating secondly; 7. removing glue and Cr/Au, and completing the manufacture. This invention has strong applied value and fit to large-scale production.
Description
Technical field
The invention belongs to the micro processing field in the semiconductor technology, particularly a kind of high depth-width ratio deep sub-micrometer, nanometer metal structure making process based on self-supporting film.
Background technology
Phase-type diffraction optical element for high accuracy X ray wave band, in order to obtain needed position phase, must make high depth-width ratio deep sub-micrometer, nanometer metal structure, as everyone knows, be subjected to resolution and electronic energy quantitative limitation, conventional electron beam lithography technology can't be made high depth-width ratio deep sub-micrometer, nanometer metal structure, if adopt electron beam lithography technology twice, not only cost height, complex process, and the overlay alignment ability of electron beam lithography machine proposed very high requirement, be difficult in actual use realize.
Summary of the invention
The purpose of this invention is to provide a kind of high depth-width ratio deep sub-micrometer, nanometer metal structure making process based on self-supporting film, it adopts once front electron beam lithography, a back side X ray self-aligned exposure, twice plating obtains high depth-width ratio deep sub-micrometer, nanometer metal structure, can satisfy the requirement of the phase-type diffraction optical element of high accuracy X ray wave band.
For achieving the above object, technical solution of the present invention provides a kind of based on the self-supporting film high depth-width ratio deep sub-micrometer, nanometer metal structure making process, its high depth-width ratio deep sub-micrometer, the formation of nanometer metal structure is by electron beam lithography, electro-plating method obtains low depth-width ratio deep-submicron earlier on self-supporting film, nanometer metal structure, on this metal structure, get rid of X-ray resist again, carry out the exposure of autoregistration X ray from the back side, continue to electroplate out high depth-width ratio deep sub-micrometer again, nanometer metal structure, remove photoresist at last, thin chromium approaches the gold layer, thereby makes the high depth-width ratio deep sub-micrometer based on self-supporting film, nanometer metal structure.
Described a kind of based on self-supporting film high depth-width ratio deep sub-micrometer, nanometer metal structure making process, comprise the steps:
Step 1, on the self-supporting film front the thin gold layer of deposit thin chromium, as electroplating the lining base;
Step 2, get rid of electron beam adhesive on the thin golden laminar surface of Bao Ge, electron beam exposure, development form the mould of electroplating for the first time;
Step 3, step 2 gained slice, thin piece is placed in the electroplate liquid plated metal for the first time;
Step 4, get rid of X-ray resist in step 3 gained slice, thin piece front;
Step 5, carry out the X ray exposure from the self-supporting film back side, develop, form the mould of electroplating for the second time;
Step 6, step 5 gained slice, thin piece is placed in the electroplate liquid plated metal for the second time;
Step 7, to step 6 gained slice, thin piece remove photoresist, the thin gold layer of thin chromium, finish high depth-width ratio deep sub-micrometer, nanometer metal structure.
Described a kind of based on self-supporting film high depth-width ratio deep sub-micrometer, nanometer metal structure making process, in the described step 1, the thin gold layer of this thin chromium is to use electron beam evaporation method to obtain, and gross thickness is 10～30nm.
Described a kind of based on self-supporting film high depth-width ratio deep sub-micrometer, nanometer metal structure making process, in its described step 2, the model of electron beam adhesive is the SAL601-ER7 that Japanese Shipley company produces, and thickness is 150～600nm, and carries out the following step: a) carry out preceding baking with hot plate; B) again electron beam adhesive is carried out electron beam exposure, dosage≤35 microcoulombs; C) the reusable heat plate carries out the back baking to electron beam adhesive; D) and then with developer solution develop developing time≤4 minute; E) after the development, wash, dry up slice, thin piece, form the mould of plated metal for the first time with nitrogen with deionized water.
Described a kind of based on self-supporting film high depth-width ratio deep sub-micrometer, nanometer metal structure making process, in its described step 3, the electroplate liquid of electroplating is a gold plating bath for the first time, form deep-submicron, the nm of gold metal structure of initial low depth-width ratio, the thickness of golden metal structure is 150～600nm.
Described a kind of based on self-supporting film high depth-width ratio deep sub-micrometer, nanometer metal structure making process, in its described step 4, X-ray resist comprises that chemistry amplifies and non-chemically amplifies two types,, thickness is 500～2000nm, and carries out preceding baking with hot plate.
Described a kind of based on self-supporting film high depth-width ratio deep sub-micrometer, nanometer metal structure making process, the concrete steps of its described step 5 are as follows: a) carry out the X ray exposure from the self-supporting film back side; B) with hot plate X-ray resist is carried out the back baking; C) develop developing time≤4 minute then with developer solution; D) after the development, wash, dry up slice, thin piece, form the mould of plated metal for the second time with nitrogen with deionized water.
Described a kind of based on self-supporting film high depth-width ratio deep sub-micrometer, nanometer metal structure making process, in its described step 6, the electroplate liquid of electroplating is a gold plating bath for the second time, forms deep-submicron, the nm of gold metal structure of high depth-width ratio, and the thickness of golden metal structure is 650～2600nm.
Described a kind of based on self-supporting film high depth-width ratio deep sub-micrometer, nanometer metal structure making process, the concrete steps of its described step 7 are as follows: a) step 6 gained slice, thin piece is placed in the acetone 9～11 minutes, removes the mould of plated metal for the first time and the mould of plated metal for the second time; B) ultrasonic cleaning in ethanol, deionized water rinsing, nitrogen dries up; C) fall the down payment of mould below with ion beam etching; D) spend the end chromium that chrome liquor removes the mould below; E) and then use deionized water rinsing, nitrogen dries up, and finishes the making of high depth-width ratio deep sub-micrometer, nanometer metal structure.
Described a kind of based on self-supporting film high depth-width ratio deep sub-micrometer, nanometer metal structure making process, the temperature of baking was 100～110 ℃ before it was described, and the time is≤2 minutes, and the temperature of described back baking is 100～110 ℃, and the time is≤2 minutes.
Characteristics of the present invention are to adopt once front electron beam lithography, a back side X ray self-aligned exposure, and twice plating obtains high depth-width ratio deep sub-micrometer, nanometer metal structure, has very strong practical value.High depth-width ratio deep sub-micrometer based on self-supporting film, the nanometer metal structure of process preparation of the present invention are suitable for producing in enormous quantities.
Description of drawings
Fig. 1-1 is to Fig. 1-the 7th, the flow chart of technology of the present invention;
Fig. 2-1 is to Fig. 2-the 9th, the flow chart of the embodiment of the invention.
Embodiment
Seeing Fig. 1, is that the present invention is a kind of based on the high depth-width ratio deep sub-micrometer of self-supporting film, the flow chart of nanometer metal structure making process, and its flow process is as follows:
1, as Figure 1-1, at first the thin gold layer 103 of deposit thin chromium on ∏ shape self-supporting film front serves as a contrast base as electroplating, and the thin gold layer 103 of this thin chromium can use electron beam evaporation method to obtain, and gross thickness is 10～30nm.
2, shown in Fig. 1-2, on the thin gold layer of Bao Ge 103 surface, get rid of electron beam adhesive, electron beam adhesive thickness is 150-600nm, uses electron beam exposure, development again, forms the mould 104 of plated metal for the first time.
3, as Figure 1-3, will go up step gained slice, thin piece and be placed in the electroplate liquid, carry out the plated metal first time, form deep-submicron, the nanometer metal structure 105a of low depth-width ratio by mould 104.
4, shown in Fig. 1-4, get rid of X-ray resist 106 in last step gained slice, thin piece front, X-ray resist 106 thickness are 500-2000nm.
5, shown in Fig. 1-5, carry out the X ray exposure from the self-supporting film back side, develop, form the mould 107 of plated metal for the second time.
6, shown in Fig. 1-6, will go up step gained slice, thin piece and be placed in the electroplate liquid, carry out the plated metal second time by mould 107, form deep-submicron, the nanometer metal structure 105b of high depth-width ratio, the gross thickness of metal structure 105b is 650-2600nm.
7, shown in Fig. 1-7, remove photoresist, go the thin chromium of mould 107 belows to approach gold layer 103 to gained slice, thin piece of last step, finish high depth-width ratio deep sub-micrometer, nanometer metal structure making.
Embodiment
1, shown in Fig. 2-1, at first deposit thin chromium approaches gold layer 203 on ∏ shape self-supporting film front, and this thin chromium can use electron beam evaporation method to obtain for thin golden layer 203, and gross thickness is 10～30nm.∏ shape self-supporting film is made up of silicon nitride film 101 and silicon chip 102, and the bottom foot is a silicon nitride film 101, and the middle part supporting leg is a silicon chip 102, and the upper end is a silicon nitride film 101.
2, shown in Fig. 2-2, on the thin gold layer of Bao Ge 203 surface, get rid of electron beam adhesive 204, electron beam adhesive 204 thickness are 150-600nm, and carry out preceding baking with hot plate, and pre-bake temperature is 105 ℃, and the preceding baking time is 2 minutes.
3, shown in Fig. 2-3, electron beam adhesive 204 is carried out electron beam exposure, dosage is 35 microcoulombs, with hot plate electron beam adhesive 204 is carried out the back baking then, and back baking temperature is 105 ℃, the back baking time is 2 minutes, develop with developer solution, developing time is 4 minutes, and the back of developing is washed with deionized water, dry up slice, thin piece with nitrogen, form the mould 205 of plated metal for the first time.
4, shown in Fig. 2-4, slice, thin piece is placed in the electroplate liquid, carry out the plated metal first time by mould 205, electroplate liquid is a gold plating bath, forms deep-submicron, the nm of gold metal structure 206a of low depth-width ratio, the thickness of golden metal structure 206a is 150-600nm.
5, shown in Fig. 2-5, get rid of X-ray resist 207 in the slice, thin piece front,, X-ray resist 207 thickness are 500-2000nm, and carry out preceding baking with hot plate, and pre-bake temperature is 105 ℃, and the preceding baking time is 2 minutes.
6, shown in Fig. 2-6, carry out the X ray exposure from the self-supporting film back side, with hot plate X-ray resist 207 is carried out the back baking then, back baking temperature is 105 ℃, and the back baking time is 2 minutes, develops with developer solution, developing time is 4 minutes, wash with deionized water after developing, dry up slice, thin piece, form the mould 208 of plated metal for the second time with nitrogen.
7, shown in Fig. 2-7, slice, thin piece is placed in the electroplate liquid, carry out the plated metal second time by mould 208, electroplate liquid is a gold plating bath, forms deep-submicron, the nm of gold metal structure 206 of high depth-width ratio, the thickness of golden metal structure 206 is 650-2600nm.
8, shown in Fig. 2-8, slice, thin piece is placed in the acetone 10 minutes, remove the mould 205 of plated metal for the first time and the mould 208 of plated metal for the second time, ultrasonic cleaning in ethanol then, deionized water rinsing, nitrogen dries up.
9, shown in Fig. 2-9, fall the down payment of mould 205 belows with ion beam etching, remove the end chromium of mould 205 belows with the liquid that dechromises of dilution, use deionized water rinsing again, nitrogen dries up, and finishes high depth-width ratio deep sub-micrometer, nanometer metal structure is made.
Claims (12)
1, a kind of based on the self-supporting film high depth-width ratio deep sub-micrometer, nanometer metal structure making process, it is characterized in that, high depth-width ratio deep sub-micrometer, the formation of nanometer metal structure is by electron beam lithography, electro-plating method obtains low depth-width ratio deep-submicron earlier on self-supporting film, nanometer metal structure, on this metal structure, get rid of X-ray resist again, carry out the exposure of autoregistration X ray from the back side, continue to electroplate out high depth-width ratio deep sub-micrometer again, nanometer metal structure, remove photoresist at last, thin chromium approaches the gold layer, thereby makes the high depth-width ratio deep sub-micrometer based on self-supporting film, nanometer metal structure.
2, according to claim 1 a kind ofly it is characterized in that, comprise the steps: based on self-supporting film high depth-width ratio deep sub-micrometer, nanometer metal structure making process
Step 1, on the self-supporting film front the thin gold layer of deposit thin chromium, as electroplating the lining base;
Step 2, get rid of electron beam adhesive on the thin golden laminar surface of Bao Ge, electron beam exposure, development form the mould of electroplating for the first time;
Step 3, step 2 gained slice, thin piece is placed in the electroplate liquid plated metal for the first time;
Step 4, get rid of X-ray resist in step 3 gained slice, thin piece front;
Step 5, carry out the X ray exposure from the self-supporting film back side, develop, form the mould of electroplating for the second time;
Step 6, step 5 gained slice, thin piece is placed in the electroplate liquid plated metal for the second time;
Step 7, to step 6 gained slice, thin piece remove photoresist, the thin gold layer of thin chromium, finish high depth-width ratio deep sub-micrometer, nanometer metal structure.
3, according to claim 2 a kind ofly it is characterized in that based on self-supporting film high depth-width ratio deep sub-micrometer, nanometer metal structure making process, in the described step 1, the thin gold layer of this thin chromium is to use electron beam evaporation method to obtain, and gross thickness is 10～30nm.
4, according to claim 2 a kind of based on self-supporting film high depth-width ratio deep sub-micrometer, nanometer metal structure making process, it is characterized in that, in the described step 2, the model of electron beam resist is the SAL601-ER7 that Japanese Shipley company produces, thickness is 150～600nm, and carries out the following step: a) carry out preceding baking with hot plate; B) again electron beam adhesive is carried out electron beam exposure, dosage≤35 microcoulombs; C) the reusable heat plate carries out the back baking to electron beam adhesive; D) and then with developer solution develop developing time≤4 minute; E) after the development, wash, dry up slice, thin piece, form the mould of plated metal for the first time with nitrogen with deionized water.
5, according to claim 2 a kind of based on self-supporting film high depth-width ratio deep sub-micrometer, nanometer metal structure making process, it is characterized in that, in the described step 3, the electroplate liquid of electroplating is a gold plating bath for the first time, form deep-submicron, the nm of gold metal structure of initial low depth-width ratio, the thickness of golden metal structure is 150～600nm.
6, according to claim 2ly a kind ofly it is characterized in that based on self-supporting film high depth-width ratio deep sub-micrometer, nanometer metal structure making process in the described step 4, X-ray resist thickness is 500～2000nm, and carries out preceding baking with hot plate.
7, according to claim 2ly a kind ofly it is characterized in that based on self-supporting film high depth-width ratio deep sub-micrometer, nanometer metal structure making process the concrete steps of described step 5 are as follows: a) carry out the X ray exposure from the self-supporting film back side; B) with hot plate X-ray resist is carried out the back baking; C) develop developing time≤4 minute then with developer solution; D) after the development, wash, dry up slice, thin piece, form the mould of plated metal for the second time with nitrogen with deionized water.
8, according to claim 2 a kind of based on self-supporting film high depth-width ratio deep sub-micrometer, nanometer metal structure making process, it is characterized in that, in the described step 6, the electroplate liquid of electroplating is a gold plating bath for the second time, form deep-submicron, the nm of gold metal structure of high depth-width ratio, the thickness of golden metal structure is 650～2600nm.
9, according to claim 2 a kind of based on self-supporting film high depth-width ratio deep sub-micrometer, nanometer metal structure making process, it is characterized in that, the concrete steps of described step 7 are as follows: a) step 6 gained slice, thin piece is placed in the acetone 9～11 minutes, removes the mould of plated metal for the first time and the mould of plated metal for the second time; B) ultrasonic cleaning in ethanol, deionized water rinsing, nitrogen dries up; C) fall the down payment of mould below with ion beam etching; D) spend the end chromium that chrome liquor removes the mould below; E) and then use deionized water rinsing, nitrogen dries up, and finishes the making of high depth-width ratio deep sub-micrometer, nanometer metal structure.
10, according to claim 5 a kind of based on self-supporting film high depth-width ratio deep sub-micrometer, nanometer metal structure making process, it is characterized in that the temperature of described preceding baking is 100～110 ℃, the time is≤2 minutes, the temperature of described back baking is 100～110 ℃, and the time is≤2 minutes.
11, according to claim 7 a kind ofly it is characterized in that based on self-supporting film high depth-width ratio deep sub-micrometer, nanometer metal structure making process, described before the temperature of baking be 100～110 ℃, the time is≤2 minutes.
12, according to claim 8 a kind ofly it is characterized in that based on self-supporting film high depth-width ratio deep sub-micrometer, nanometer metal structure making process, the temperature of described back baking is 100～110 ℃, and the time is≤2 minutes.
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| CN101520600B (en) * | 2008-02-27 | 2011-06-01 | 中国科学院微电子研究所 | Method for preparing transparent nano imprinting template based on X-ray exposure technology |
| CN102466832B (en) * | 2010-11-12 | 2013-09-11 | 中国科学院微电子研究所 | Method for manufacturing photon sieve with high height-width ratio |
| CN102608862A (en) * | 2011-01-19 | 2012-07-25 | 中国科学院微电子研究所 | Method for producing device in structure with large height-to-width ratio |
| CN106933054B (en) * | 2015-12-31 | 2019-12-24 | 上海微电子装备（集团）股份有限公司 | Graphical process method |
| CN106094445B (en) * | 2016-06-12 | 2018-11-20 | 中国科学院微电子研究所 | The production method of large ratio of height to width nano level metal structure |
| CN108557754B (en) * | 2018-04-13 | 2020-11-10 | 杭州电子科技大学 | Preparation method of self-supporting metal nano-pore film |
| CN110970147B (en) * | 2019-11-07 | 2022-11-18 | 复旦大学 | High-resolution hard X-ray tungsten/gold Fresnel zone plate and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4018938A (en) * | 1975-06-30 | 1977-04-19 | International Business Machines Corporation | Fabrication of high aspect ratio masks |
| US5178975A (en) * | 1991-01-25 | 1993-01-12 | International Business Machines Corporation | High resolution X-ray mask having high aspect ratio absorber patterns |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4018938A (en) * | 1975-06-30 | 1977-04-19 | International Business Machines Corporation | Fabrication of high aspect ratio masks |
| US5178975A (en) * | 1991-01-25 | 1993-01-12 | International Business Machines Corporation | High resolution X-ray mask having high aspect ratio absorber patterns |
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Assignee: KUNSHAN MICROOPTIC ELECTRONIC CO.,LTD. Assignor: Institute of Microelectronics of the Chinese Academy of Sciences Contract record no.: 2011320010027 Denomination of invention: High depth-width ratio deep sub-micrometer, nanometer metal structure making process based on self-supporting thin film Granted publication date: 20090304 License type: Common License Open date: 20060712 Record date: 20110325 |
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Owner name: INST OF MICROELECTRONICS, C. A. S Effective date: 20130419 Owner name: SEMICONDUCTOR MANUFACTURING INTERNATIONAL (SHANGHA Free format text: FORMER OWNER: INST OF MICROELECTRONICS, C. A. S Effective date: 20130419 |
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