CN1945799A - Graphic method for semiconductor device copper electrode - Google Patents
Graphic method for semiconductor device copper electrode Download PDFInfo
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- CN1945799A CN1945799A CN 200610150978 CN200610150978A CN1945799A CN 1945799 A CN1945799 A CN 1945799A CN 200610150978 CN200610150978 CN 200610150978 CN 200610150978 A CN200610150978 A CN 200610150978A CN 1945799 A CN1945799 A CN 1945799A
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Abstract
This invention provides a pattern method for a copper electrode of a semiconductor device, which grows a diffused blocking layer on the base of a semiconductor and grows Cu film and its alloy films on the diffused blocking layer, anneals the semiconductor chip in a protection atmosphere then reduces the temperature to room temperature steadily, coats an etch glue on the Cu film then dips the being eroded semiconductor chip with figures in an erosion solution at a temperature, then, flushes the chip with deionised water and strips it in a stripping solution to be processed by triclene and methyl alcohol.
Description
(1) technical field
The invention belongs to the semiconductor device fabrication field, particularly a kind of graphic method of semiconductor device copper electrode.
(2) background technology
Cu is owing to having the substitution material that low resistivity and high deelectric transferred ability can be used as Al.Employing Cu electrically contacts as semi-conductor discrete device, because the Cu high thermal reaches and the heat sink consistent thermal coefficient of expansion of Cu, helps to reduce the thermal resistance of electric contact-system and the reliability that improves device.Damascus technics is the graphical technology of copper (the Steinbr ü chel during a kind of integrated circuit is made, C.Patterning of copper for multilevel metallization:Reactive ion etching andchemical-mechanical polishing.Applied Surface Science, 91 (1995) 139-146.), but because when chemico-mechanical polishing (CMP) is handled, owing to the Cu film is crossed throwing and pit occurred.Simultaneously, the particle that exists in the CMP polishing fluid can embed its resistivity is increased.Publication US6,010,603 utilizes the physical bombardment of high energy and high density ion to reach purpose to Cu film etching, but this needs the extra equipment that produces high energy and high density ion, the underlayer temperature of also will taking measures to keep simultaneously.Publication US5,736,002 adopt will be to be removed Cu form chloride or oxide earlier, again with the method for chloride or the oxide removal of Cu.Publication JP59100300 then adopts electrochemical etching method to realize the graphical of copper film.But above-mentioned two kinds of methods have also increased the complex process degree when needing extras equally.Publication CN1614076 adopts patterned stainless steel thin slice as masterplate, through flaky magnet with its adsorbed close above silicon chip, by the method for magnetically controlled DC sputtering, once property obtains patterned electrode on silicon chip at last.But the minimum of this masterplate is existing wide to be 0.2mm, is mainly used in the electrode pattern metallization processes of ferroelectric thin film device, inapplicable for the semiconductor device that live width is very little.
(3) summary of the invention
The object of the present invention is to provide a kind of simple have applied widely, need not special process and special installation, cheap, the advantage of high production efficiency of cost of manufacture, the graphic method of the semiconductor device copper electrode that is easy to promote the use of.
The object of the present invention is achieved like this: the diffusion impervious layer of growing on the semiconductor-based end, and grow on diffusion impervious layer Cu film or Cu alloy film; With gained semiconductor chip annealing in process in protective atmosphere, reduce to room temperature then.Spin coating photoresist on Cu film or Cu alloy film, after photo-mask process is handled, will waiting to lose in the rotten semiconductor chip immersion corrosive liquid and corrode with figure; Then, the semiconductor chip that takes out is rinsed well with deionized water, put into stripper and remove photoresist, handle through trichloroethylene and methyl alcohol successively then.
The present invention also has such technical characterictic:
1, described diffusion impervious layer is the skim diffusion impervious layer that utilizes the method growth of PVD, CVD or ALD on semiconductor chip, and the thickness of this thin layer is at 10~300nm;
2, described diffusion impervious layer is Ti, Ta, Zr, W, Mo insoluble metal and binary and ternary nitride;
3, described Cu film or Cu alloy film are Cu film or the Cu alloy films that the semiconductor chip behind the growth diffusion impervious layer is utilized CVD, PVD or electric plating method growth, and thickness is at 200~2000nm;
4, to be Cu with solid solubility therein not high and formed alloy films such as the element that can separate out at crystal boundary such as Sn, Mg, Al, Cr, Zr for described Cu alloy film;
5, the semiconductor chip that will grow behind Cu film or the Cu alloy film was annealed 40-60 minute in 400-500 ℃ protective atmosphere, reduced to room temperature then;
Semiconductor chip when 6, the described semiconductor-based end is for the making semiconductor device before the metallization;
7, described protective atmosphere is N
2Atmosphere, Ar atmosphere or N
2/ H
2(9: 1) mixed atmosphere.
8, semiconductor chip to be corroded is upper and lower in corrosive liquid makes spinning motion in mobile.
The present invention's diffusion impervious layer of at first growing on semiconductor chip at growth Cu film or Cu alloy film, utilizes photoresist to form figure by photo-mask process then, and the semiconductor chip that will have figure is put into the electrode pattern that corrosive liquid forms needs.Wherein, diffusion impervious layer can be refractory metal and binary or ternary nitride such as Ti, Ta, Zr, W, Mo, can to be Cu with solid solubility therein not high and formed alloy films such as the element that can separate out at crystal boundary such as Sn, Mg, Al, Cr, Zr for the Cu alloy film, Cu alloy film (adding the very little alloying element of solid solubility) makes alloying element separate out at the interface after annealing in process, both can improve the anti-electromigration ability of Cu film, its resistivity can obviously not increased.Simultaneously, also satisfy the Cu interconnection graphization for the high requirement of Cu film dynamic performance.Described corrosive liquid is chosen according to the character of Cu film, Cu alloy film and following diffusion impervious layer thereof, and the temperature of corrosive liquid is selected by corrosive liquid Cu film and following diffusion impervious layer corrosion rate thereof to be designed.Adopt method provided by the present invention simple to operate, with low cost, need not special process and special installation, production efficiency height, be applicable to and make semiconductor device metal electrode commonly used particularly Cu electrode or Cu alloy electrode, be easy to promote the use of.
(4) description of drawings
Fig. 1-Fig. 4 is the operation chart of the embodiment of the invention.
(5) embodiment
Describe content of the present invention in detail below in conjunction with embodiment and accompanying drawing:
Embodiment 1:
(1) the cleaning clean is treated rotten silicon chip 1 routinely, puts into the reative cell of superhigh vacuum magnetron sputtering equipment after drying up with nitrogen;
(2) in conjunction with Fig. 1, on silicon chip 1, utilize the method growth skim ZrN diffusion impervious layer 2 of magnetically controlled DC sputtering, the THICKNESS CONTROL of this thin layer is at 200 ± 10nm;
(3) in conjunction with Fig. 2, step 2 gained semiconductor chip is utilized the method growth in situ Cu film 3 of magnetically controlled DC sputtering, film thickness monitoring is at 2000 ± 50nm;
(4) with step 3 gained semiconductor chip at 400 ℃, N
2/ H
2The 60min that anneals in (volume ratio is 9: 1) mixed atmosphere slowly reduces to room temperature then;
(5),, be placed on the hot plate about 40 seconds then with step 4 gained semiconductor chip spin coating BN308 type photoresist 4 in conjunction with Fig. 2; Through under 135 ℃ of conditions, utilizing mask plate 5 post bakes 30 minutes after overexposure, development and the photographic fixing again, obtain the photoresist figure consistent with electrode pattern;
(6), step 5 gained semiconductor chip is immersed corrosive liquid (10HNO in conjunction with Fig. 3
3: 1H
2O) in, use the heating tank that can control temperature, temperature is generally 45 ± 1 ℃, by temperature controller control temperature, semiconductor chip is upper and lower in corrosive liquid makes spinning motion in mobile, corrodes after about 10 minutes and takes out, clean with a large amount of deionized water rinsings;
(7) step 6 gained semiconductor chip is immersed dense H
2SO
4In, use the heating tank that can control temperature, temperature is generally 45 ± 1 ℃, by temperature controller control temperature, semiconductor chip is upper and lower in corrosive liquid makes spinning motion in mobile, corrodes after about 5 minutes and takes out, clean with a large amount of deionized water rinsings;
(8) in conjunction with Fig. 4, will remove photoresist in the step 7 gained semiconductor chip immersion stripper, the temperature of stripper is controlled at 100 ± 5 ℃, need change liquid 3 times.(75 ± 5 ℃ are changed liquid 2 times to pass through trichloroethylene after the taking-up successively; Change liquid under the room temperature 2 times) and methyl alcohol processing (changing liquid under the room temperature 2 times).
Embodiment 2:
(1) the cleaning clean is treated rotten silicon chip 1 routinely, puts into the reative cell of superhigh vacuum magnetron sputtering equipment after drying up with nitrogen;
(2) in conjunction with Fig. 1, on silicon chip 1, utilize the method growth skim Mo diffusion impervious layer 2 of magnetically controlled DC sputtering, the THICKNESS CONTROL of this thin layer is at 300 ± 20nm;
(3) in conjunction with Fig. 2, step 2 gained semiconductor chip is utilized the method growth in situ Cu and the Zr alloy film 3 of magnetically controlled DC sputtering, film thickness monitoring is at 1000 ± 30nm;
(4) with step 3 gained semiconductor chip at 500 ℃, N
2/ H
2Annealing is 40 minutes in (volume ratio is 9: 1) mixed atmosphere, slowly reduces to room temperature then;
(5),, be placed on hot plate last 40 second then with step 4 gained semiconductor chip spin coating BN308 type photoresist 4 in conjunction with Fig. 2; Through under 135 ℃ of conditions, utilizing mask plate 5 post bakes 30 minutes after overexposure, development and the photographic fixing again, obtain the photoresist figure consistent with electrode pattern;
(6), step 5 gained semiconductor chip is immersed corrosive liquid (10HNO in conjunction with Fig. 3
3: 1H
2O) in, use the heating tank that can control temperature, temperature is 45 ℃, and by temperature controller control temperature, semiconductor chip is upper and lower in corrosive liquid makes spinning motion in mobile, corrode taking-up after 10 minutes, clean with a large amount of deionized water rinsings;
(7) step 6 gained semiconductor chip is immersed dense H
2SO
4In, use the heating tank that can control temperature, temperature is 45 ℃, by temperature controller control temperature, semiconductor chip is upper and lower in corrosive liquid makes spinning motion in mobile, corrode taking-up after 5 minutes, clean with a large amount of deionized water rinsings;
(8) in conjunction with Fig. 4, will remove photoresist in the step 7 gained semiconductor chip immersion stripper, the temperature of stripper is controlled at 100 ℃, need change liquid 3 times.(75 ± 5 ℃ are changed liquid 2 times to pass through trichloroethylene after the taking-up successively; Change liquid under the room temperature 2 times) and methyl alcohol processing (changing liquid under the room temperature 2 times).
Claims (9)
1, a kind of graphic method of semiconductor device copper electrode is characterized in that: the diffusion impervious layer of growing on the semiconductor-based end, and grow on diffusion impervious layer Cu film or Cu alloy film; With gained semiconductor chip annealing in process in protective atmosphere, reduce to room temperature then.Spin coating photoresist on Cu film or Cu alloy film, after photo-mask process is handled, will waiting to lose in the rotten semiconductor chip immersion corrosive liquid and corrode with figure; Then, the semiconductor chip that takes out is rinsed well with deionized water, put into stripper and remove photoresist, handle through trichloroethylene and methyl alcohol successively then.
2, the graphic method of semiconductor device copper electrode according to claim 1, it is characterized in that: described diffusion impervious layer is the skim diffusion impervious layer that utilizes the method growth of PVD, CVD or ALD on semiconductor chip, and the thickness of this thin layer is at 10~300nm.
3, the graphic method of semiconductor device copper electrode according to claim 2 is characterized in that: described diffusion impervious layer is Ti, Ta, Zr, W, Mo insoluble metal and binary and ternary nitride.
4, the graphic method of semiconductor device copper electrode according to claim 3, it is characterized in that: described Cu film or Cu alloy film are Cu film or the Cu alloy films that the semiconductor chip behind the growth diffusion impervious layer is utilized CVD, PVD or electric plating method growth, and thickness is at 200~2000nm.
5, the graphic method of semiconductor device copper electrode according to claim 4 is characterized in that: to be Cu with solid solubility therein not high and formed alloy films such as the element that can separate out at crystal boundary such as Sn, Mg, Al, Cr, Zr for described Cu alloy film.
6, the graphic method of semiconductor device copper electrode according to claim 5 is characterized in that: the semiconductor chip behind will grow Cu film or the Cu alloy film was annealed 40-60 minute in 400-500 ℃ protective atmosphere, reduced to room temperature then.
7, the graphic method of semiconductor device copper electrode according to claim 6 is characterized in that: the described semiconductor-based end is the semiconductor chip before the metallization when making semiconductor device.
8, the graphic method of semiconductor device copper electrode according to claim 7 is characterized in that: described protective atmosphere is N
2Atmosphere, Ar atmosphere or N
2/ H
2(9: 1) mixed atmosphere.
9, the graphic method of semiconductor device copper electrode according to claim 8 is characterized in that: semiconductor chip to be corroded is upper and lower in corrosive liquid makes spinning motion in mobile.
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Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101794861A (en) * | 2009-01-29 | 2010-08-04 | 索尼公司 | Semiconductor storage and manufacture method thereof |
CN102005384A (en) * | 2010-09-16 | 2011-04-06 | 哈尔滨工程大学 | Method for low temperature annealing of copper metallized self-formed barrier layer |
CN103058126A (en) * | 2012-11-30 | 2013-04-24 | 北京遥测技术研究所 | Processing method for surface electrodes of three-dimensional quartz micro-mechanical structure |
CN106816375A (en) * | 2015-11-30 | 2017-06-09 | 英飞凌科技奥地利有限公司 | Semiconductor devices and the method for forming semiconductor devices |
CN109553066A (en) * | 2018-11-20 | 2019-04-02 | 上海交通大学 | A kind of method of nano material plasma surface transformation |
WO2020118984A1 (en) * | 2018-12-13 | 2020-06-18 | 深圳市华星光电半导体显示技术有限公司 | Array substrate preparation method |
-
2006
- 2006-11-01 CN CNB2006101509781A patent/CN100508129C/en not_active Expired - Fee Related
Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101794861A (en) * | 2009-01-29 | 2010-08-04 | 索尼公司 | Semiconductor storage and manufacture method thereof |
CN102005384A (en) * | 2010-09-16 | 2011-04-06 | 哈尔滨工程大学 | Method for low temperature annealing of copper metallized self-formed barrier layer |
CN102005384B (en) * | 2010-09-16 | 2012-02-01 | 哈尔滨工程大学 | Method for low temperature annealing of copper metallized self-formed barrier layer |
CN103058126A (en) * | 2012-11-30 | 2013-04-24 | 北京遥测技术研究所 | Processing method for surface electrodes of three-dimensional quartz micro-mechanical structure |
CN103058126B (en) * | 2012-11-30 | 2015-11-25 | 北京遥测技术研究所 | A kind of processing method of three-dimensional quartz micro mechanical structure surface electrode |
CN106816375A (en) * | 2015-11-30 | 2017-06-09 | 英飞凌科技奥地利有限公司 | Semiconductor devices and the method for forming semiconductor devices |
US10332793B2 (en) | 2015-11-30 | 2019-06-25 | Infineon Technologies Austria Ag | Self-organizing barrier layer disposed between a metallization layer and a semiconductor region |
CN106816375B (en) * | 2015-11-30 | 2020-12-08 | 英飞凌科技奥地利有限公司 | Semiconductor device and method of forming a semiconductor device |
CN109553066A (en) * | 2018-11-20 | 2019-04-02 | 上海交通大学 | A kind of method of nano material plasma surface transformation |
WO2020118984A1 (en) * | 2018-12-13 | 2020-06-18 | 深圳市华星光电半导体显示技术有限公司 | Array substrate preparation method |
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