CN100459057C - Cleaning method of crystal column surface - Google Patents
Cleaning method of crystal column surface Download PDFInfo
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- CN100459057C CN100459057C CNB2006100267573A CN200610026757A CN100459057C CN 100459057 C CN100459057 C CN 100459057C CN B2006100267573 A CNB2006100267573 A CN B2006100267573A CN 200610026757 A CN200610026757 A CN 200610026757A CN 100459057 C CN100459057 C CN 100459057C
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- column surface
- crystal column
- propylene glycol
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Abstract
The invention discloses a cleaning method of round crystal surface, which uses photo-etching gel quantity reducing consumer to clean the round crystal surface to remove the photo-etching gel quantity reducing consumer from the round crystal surface. The invention also provides a new application of photo-etching gel quantity reducing consumer as the cleaning agent of round crystal surface, which can be used in the spraying course to do photo-etch directly without leading other pollution, in order to save the RRC abluent price and cost.
Description
Technical field
The present invention relates to a kind of cleaning method of crystal column surface, more precisely is the cleaning method of crystal column surface before the spraying photoresist in lithographic process.
Background technology
Wafer and behind each treatment step, all can stay pollutant usually on wafer in the process of storage, loading and unloading, as particle, and metal ion, organic substance etc.Different pollutants need adopt different cleaning methods.Organic impurities pollutes and can remove in conjunction with ultrasonic cleaning technology by the dissolution of organic solvent; Particle pollutes the particle that the method can use physics such as mechanical scrub or the clear wave technology of ultrasonic wave remove particle diameter 〉=0.4 μ m, utilizes mega sonic wave can remove 〉=particle of 0.2 μ m.At present industry the method that clears the pollution off of extensive employing be to use SC1 cleaning fluid (NH
4OH/H
2O
2/ H
2O=1: 1: 5) and SC2 cleaning fluid (HCL/H
2O
2/ H
2O=1: 1: 6), organic substance and particle contamination can not only be removed, also metal ion pollution can be better removed.Wafer can utilize SC1 cleaning fluid and SC2 cleaning fluid to remove pollutants such as the organic substance on surface, metallic particles usually, but this method relative cost is higher before entering lithographic process.
For reducing cost and saving the consideration of production cycle, some processing procedures before wafer enters lithographic process do not use SC1 cleaning fluid and SC2 cleaning fluid, but adopt the method for deionized water rinsing.Providing a kind of cleaning method of wafer as Chinese patent CN02131868, mainly is after crystal column surface forms the layer of material layer, and this wafer is carried out scrubbing technology.Supply with earlier deionized water to crystal column surface, and after scrubbing crystal column surface with brush, when drying is attached to the deionized water of crystal column surface, with the blowing inert gas crystal column surface.But utilize after this method cleans crystal column surface, can not remove the pollutant of crystal column surface completely, these pollutants are brought into after the jet-coating photoresit processing procedure, also can cause litho pattern to lose efficacy.
In film deposition process as depositing metal layers (metal) and deposit dielectric insulating barrier (IntermetalDielectric; IMD) in the process, except producing metallic particles, also can produce the organic pollutants that some main components are carbon.Prior art generally all is that the crystal column surface after adopting the plasma water process of washing to thin film deposition process cleans, and this cleaning method can only be removed the metallic particles of crystal column surface, can not remove the organic pollutants of crystal column surface fully.If these organic pollutants enter lithographic process, also can produce the inefficacy of crystal column surface litho pattern.
Wafer enters after the lithographic process, before the spraying photoresist, also need spray primer at crystal column surface, makes crystal column surface become hydrophobicity from hydrophily, to help the coating of next step photoresist.Modal primer is hexamethyldisilane (HMDS).After the spraying primer, can carry out a process of curing (bake) thereupon.Fig. 1 is the reaction principle figure that cures primer and crystal column surface generation chemical reaction in the process.As can be seen from the figure, cure primer and crystal column surface generation chemical reaction in the process, generate the accessory substance ammonia simultaneously, produce ammonia and pollute.
Because ammonia meeting and H
+Reaction, the ammonia of generation can consume the H in the photoresist
+And H
+Be deep ultra violet (DUV) photoresist catalyst for reaction, if there is not H
+, photoresponse will can not take place in photoresist.Fig. 2 a is that ammonia pollutes the structural representation cause negative photoresist to lose efficacy, and shown in Fig. 2 a, ammonia pollutes 1 makes the negative photoresist 2 will formation figure v notch v at crystal column surface, finally causes the inefficacy of litho pattern.Fig. 2 b is that ammonia pollutes the structural representation cause positive photoetching rubber to lose efficacy, and shown in Fig. 2 b, ammonia pollutes 1, and to make positive photoetching rubber 3 form glue at crystal column surface residual 1, and finally causes the inefficacy of litho pattern.
Because polluting, ammonia in the photoetching district, produces, if use SC1 cleaning fluid and SC2 cleaning fluid to clean, perhaps directly use the deionized water process of washing, certainly will destroy the photoresist primer of crystal column surface, and need proceed to be coated with the technology of primer, thereby continue to introduce the pollution of ammonia.Therefore, the cleaning of existing crystal column surface can't be used to remove the ammonia pollution of crystal column surface.
The general now method that installs chemical gas filter (chemical filter) additional that adopts is controlled the ammonia pollution, but not only there is the problem of inefficacy in filter, and the ammonia pollution can only be controlled within the certain level, smaller for some live widths, figure is than the photoresist layer of comparatively dense, ammonia can not be filtered out fully, still can cause the inefficacy of litho pattern.
Summary of the invention
Defective at prior art, the technical problem to be solved in the present invention provides a kind of cleaning method of crystal column surface, avoid the organic contamination that produces in the organic pollutants that still exist through crystal column surface after the deionized water rinsing before the lithographic process such as the film deposition process, and the ammonia of pollution that produces in the photoetching district such as crystal column surface pollutes the litho pattern that causes and lost efficacy.
On the other hand, the invention provides the new application of photoresist decrement agent as the crystal column surface cleaning reagent.
For addressing the above problem, the invention provides a kind of cleaning method of crystal column surface, comprise making decrement depleting agents (reduced resist consumption with photoresist; RRC) crystal column surface is cleaned, then the step of removing from crystal column surface.The agent of this photoresist decrement can directly begin to spray the processing procedure of photoresist at crystal column surface after crystal column surface is removed.
Above-mentioned photoresist decrement depleting agents can be the mixture of a kind of in propylene glycol monomethyl ether (PGME), acetate propylene glycol methyl esters (PGMEA), OK73 diluent, cyclohexanone (Cyclohexanone), the gamma-butyrolacton (Gamma-Butyrolactone) or two kinds.
The photoresist decrement depleting agents of comparative optimization is the OK73 diluent, it is the mixture of single ethylether propylene glycol and propylene glycol methyl ether acetate, the mass percent of wherein single ethylether propylene glycol is 70%, and the mass percent of propylene glycol methyl ether acetate is 30%.
The cleaning method of above-mentioned crystal column surface can use the cleaning equipment of any routine to carry out.As a kind of preferred cleaning equipment, the cleaning method of crystal column surface provided by the invention, the processing procedure of cleaning can use the equipment of spraying photoresist to carry out.As (the Tokyo Electron Limited of Tokyo Electronics Co., Ltd; TEL company) and screen limited company (Dainppon Screen MFG.CO, LTD; DNS company) the jet-coating photoresit developing apparatus (Track) of Sheng Chaning.Use above-mentioned Track to carry out cleaning provided by the invention, do not need equipment is carried out any improvement, only need increase the processing step that cleans before described Track equipment spraying photoresist gets final product, on described Track equipment, needing increases the cleaning that 2 processing steps are finished crystal column surface: after the mechanical arm of Track equipment is ready to, under the situation of wafer rotation, described RRC is sprayed on crystal column surface, the surface of wafer is cleaned; By the high speed rotating of wafer, dispose the RRC of crystal column surface then.Can directly carry out the spraying processing procedure of photoresist then.
Above-mentioned photoresist decrement depleting agents (RRC) is often used as the reagent that can save the photoresist consumption at present, it mainly is the organic solvent of the wetting photoresist of a kind of energy, before shooing out, shoots out photoresist surface earlier at wafer, perhaps on Track equipment, be sprayed on the surface of wafer with photoresist, can reduce the consumption of photoresist, save cost.
The present invention uses the cleaning reagent of above-mentioned photoresist decrement depleting agents (RRC) as crystal column surface.Both can directly clean, and also can directly use jet-coating photoresit equipment that crystal column surface is cleaned, and can effectively eliminate the ammonia pollution and the residual organic pollution of crystal column surface crystal column surface.
Beneficial effect of the present invention:
1. make with photoresist that the decrement depleting agents cleans crystal column surface, the step of removing from crystal column surface can effectively be removed the organic contamination that ammonia that wafer produces in the photoetching district pollutes and produces film deposition process then, avoids the inefficacy of litho pattern.
2. use method provided by the invention, directly use jet-coating photoresit equipment that crystal column surface is cleaned, complete the combining of spraying processing procedure with manufacturing process for cleaning and photoresist, and do not need after cleaning crystal column surface is carried out conventional dried, also need not transfer table, can directly carry out the spraying processing procedure of photoresist, avoid after manufacturing process for cleaning, introduce other pollution in the process before the jet-coating photoresit.
3. make with photoresist that decrement depleting agents (RRC) has good compatibility as the cleaning reagent of crystal column surface with photoresist, to crystal column surface and the processing procedure that sprays photoresist subsequently can not produce any pollutant.
4. employed photoresist decrement depleting agents consumption is few, cheap, and cost is lower.
Description of drawings
Fig. 1 is the reaction principle figure of primer and crystal column surface generation chemical reaction in the process of curing.
Fig. 2 a is that ammonia pollutes the structural representation that causes negative photoresist to lose efficacy.
Fig. 2 b is that ammonia pollutes the structural representation that causes positive photoetching rubber to lose efficacy.
Fig. 3 a and 3b are the wafer defect distribution maps that ammonia pollutes.
Fig. 4 a is that ammonia pollutes the wafer defect figure that causes positive photoetching rubber to lose efficacy and form.
Fig. 4 b is that ammonia pollutes the wafer defect figure that causes negative photoresist to lose efficacy and form.
Fig. 5 a and 5b are the wafer defect distribution maps that the ammonia behind employing the present invention pollutes.
Fig. 6 is the wafer defect distribution map of metal film organic pollutants.
The intensive graph area wafer defect figure that Fig. 7 a causes for the metal film organic contamination.
The sparse graph area wafer defect figure that Fig. 7 b causes for the metal film organic contamination.
Fig. 8 is the wafer defect distribution map of the metal film organic contamination behind employing the present invention.
Embodiment
The present invention has provided a kind of cleaning method of crystal column surface, comprises making with photoresist that the decrement running stores clean crystal column surface, then the step of removing from crystal column surface.The agent of this photoresist decrement can directly begin to spray the processing procedure of photoresist at crystal column surface after crystal column surface is removed.The present invention will be described in detail below in conjunction with concrete execution mode.
Identical with any existing cleaning method, cleaning method provided by the invention can use the cleaning equipment of any routine and method to carry out.Cleaning machine with routine is an example: at first, the wafer that provides a desire to clean places on the cleaning machine.This cleaning machine for example is single channelization ablution groove of hydro-peening formula or the ablution groove with concentration of lotion control device.Then with RRC cleaning fluid such as OK73 through pipeline transmission to cleaning machine, wafer is cleaned; Subsequently the RRC cleaning fluid of crystal column surface remnants is removed.Described OK73 diluent is the mixture of single ethylether propylene glycol and propylene glycol methyl ether acetate, and the mass percent of wherein single ethylether propylene glycol is 70%, and the mass percent of propylene glycol methyl ether acetate is 30%.
The consumption of OK73 diluent can clean up crystal column surface between 15ml～30ml.
The present invention can directly use the cleaning equipment of jet-coating photoresit equipment as crystal column surface, and crystal column surface is cleaned.As a kind of technical scheme of comparative optimization, method of the present invention can go up at the jet-coating photoresit developing apparatus ACT8Track that company of Tokyo Electronics Inc. (Tokyo Electron Limited.) produces and realize, and need not equipment is done any improvement.This preferred embodiment the spraying processing procedure of the manufacturing process for cleaning of wafer and photoresist being combined carries out.When using ACT8 Track that crystal column surface is cleaned, only need on the standard processing procedure spraying photoresist program of ACT8 Track equipment, add cleaning step provided by the invention and get final product.
Wafer is placed on the platform of ACT8 Track, carries out the preparation of mechanical arm, after preparation is finished, can begin to carry out manufacturing process for cleaning of the present invention.Whole manufacturing process for cleaning can divide following two steps to finish: the first step, under the situation of wafer rotation,, simultaneously wafer is cleaned from shooing out cleaning agent in the nozzle to crystal column surface.The time that speed that can be by changing the wafer rotation and RRC cleaning agent shoot out, improve the effect of cleaning.
The rotary speed of wafer is between 100～5000rpm, when rotary speed is 100rpm, wafer has had certain rotary speed, increasing along with the wafer rotary speed, the dynamics of flushing is strengthened, and developing result also improves, and the rotary speed of wafer can be selected 1000rpm, 1500rpm etc. can dispose the pollutant of crystal column surface.The rotary speed of comparative optimization can obtain best cleaning performance between 2000～3000rpm.The time of cleaning is at 5～50 seconds, because had a certain amount of RRC to be sprayed on crystal column surface during 5s, wafer washed, and the washing time of comparative optimization is between 10～20 seconds.
Generally speaking, the flow of RRC cleaning agent is 1.5ml/second in the nozzle of ACT8 Track, so by the rotary speed of control wafer and the time of cleaning, just can control the consumption of the RRC cleaning agent of use, the consumption of the RRC cleaning agent of comparative optimization is between 15～30ml.
Above-mentioned RRC cleaning agent can be the mixture of a kind of in propylene glycol monomethyl ether (PGME), acetate propylene glycol methyl esters (PGMEA), OK73 diluent, cyclohexanone (Cyclohexanone), the gamma-butyrolacton (Gamma-Butyrolactone) or two kinds.
The RRC cleaning agent of comparative optimization is the OK73 diluent, and it is the mixture of single ethylether propylene glycol and propylene glycol methyl ether acetate, and the mass percent of wherein single ethylether propylene glycol is 70%, and the mass percent of propylene glycol methyl ether acetate is 30%.
Second step, treat that the first step cleans up crystal column surface after, adjust the rotating speed of ACT8 Track, by the wafer rotation, the RRC cleaning agent that crystal column surface is unnecessary is removed.The rotary speed of wafer between 100～5000rpm, the rotary speed of comparative optimization between 2000～3000rpm, the time between 5～30 seconds, comparative optimization be between 10～20 seconds.
After by above-mentioned step crystal column surface being cleaned up, directly carry out remaining standard photoresist spray procedure of ACT8 Track, use the wetting crystal column surface of RRC of standard volume earlier, spray photoresist then at crystal column surface, and photoresist is coated on the wafer uniformly by high speed rotating, finish the spraying processing procedure of photoresist.
Under following process conditions crystal column surface is cleaned: use ACT8 Track, the rotary speed that the first step is adjusted wafer is 2000rpm, and as cleaning agent, the flow of OK73 cleaning agent is 1.5ml/second with OK73, and scavenging period is 10 seconds; The rotary speed of wafer is 3000rpm in second step, and the time is 8 seconds.Fig. 5 a and Fig. 5 b have provided the defect map of using above-mentioned cleaning method crystal column surface to be cleaned the back crystal column surface.Fig. 3 a, Fig. 3 b, Fig. 4 a and Fig. 4 b have provided crystal column surface because ammonia pollutes the microdefect figure that is not eliminated the crystal column surface that causes, wherein Fig. 3 a and Fig. 3 b are the defect map of the crystal column surface that polluted by ammonia, and Fig. 4 a and Fig. 4 b are for to carry out the defective picture that electron microscope is taken pictures by the defect map of Fig. 3 a and Fig. 3 b.As can be seen from the figure, after crystal column surface cleaned, dispose all contaminants of crystal column surface basically, avoided in lithographic process, producing the defective of lithographic images.
Fig. 3 a, Fig. 3 b, Fig. 5 a and Fig. 5 b use 8 inches wafer to detect on the KLA tencor AIT-XP equipment of U.S. section sky China company, and the electron microscope defective that Fig. 4 a and Fig. 4 b are to use company of Applied Materials to produce is taken pictures, and board SEM-vision CX obtains.
Fig. 6, Fig. 7 a and Fig. 7 b have provided crystal column surface because the metal film organic pollutants are not eliminated the microdefect figure of the crystal column surface that causes, wherein Fig. 6 is the defect map of the crystal column surface of metal film organic pollutants, and Fig. 7 a and 7b are for to carry out the defective picture that electron microscope is taken pictures by the defect map of Fig. 6.Use screen limited company (Dainppon Screen MFG.CO, LTD; DNS company) the DNS RF3 Track of Sheng Chaning, exist the crystal column surface of metal film organic pollutants (microcosmic detects picture shown in Fig. 6, Fig. 7 a and Fig. 7 b) to clean to the surface, concrete technology is: the rotary speed of wafer is 2500rpm in the first step of setting manufacturing process for cleaning, with propylene glycol monomethyl ether (PGME) as cleaning agent, the flow of propylene glycol monomethyl ether cleaning agent is 1.5ml/second, and scavenging period is 15 seconds; The rotary speed of wafer is 3000rpm in second step, and the time is 10 seconds.Detect the crystal column surface after cleaning.Fig. 8 has provided the defect map of crystal column surface being cleaned the back crystal column surface.As can be seen from the figure, cleaning method provided by the invention can effectively be removed the pollutant that crystal column surface causes owing to thin film deposition, thereby avoids because the situation that the litho pattern that the pollutant that thin film deposition causes causes lost efficacy.
Fig. 6 and Fig. 8 use 8 inches wafer to detect on the KLA tencor AIT-XP equipment of U.S. section sky China company, and the electron microscope defective that Fig. 7 a and Fig. 7 b are to use company of Applied Materials to produce is taken pictures, and board SEM-vision CX obtains.
Though the present invention with a preferred embodiment openly as above; but it is not in order to limit the present invention; any personnel that are familiar with this technology; without departing from the spirit and scope of the present invention; various changes and the retouching done; all do not break away from protection scope of the present invention, and protection scope of the present invention should be with being as the criterion that claims were limited.
Claims (11)
1. the cleaning method of a crystal column surface, it is characterized in that: organic contamination that produces in film deposition process before using a kind of or two kinds of admixture solvents in propylene glycol monomethyl ether, acetate propylene glycol methyl esters, OK73 diluent, cyclohexanone and the gamma-butyrolacton to the crystal column surface lithographic process and the ammonia that produces in the photoetching district pollute and clean, and remove described solvent from crystal column surface then.
2. the cleaning method of crystal column surface according to claim 1, it is characterized in that: described OK73 diluent, it is the mixture of single ethylether propylene glycol and propylene glycol methyl ether acetate, the mass percent of wherein single ethylether propylene glycol is 70%, and the mass percent of propylene glycol methyl ether acetate is 30%.
3. the cleaning method of crystal column surface according to claim 1, the consumption that it is characterized in that described solvent is 15ml～30ml.
4. the cleaning method of a crystal column surface is characterized in that: use jet-coating photoresit equipment that crystal column surface is cleaned, processing step is:
The first step: under the situation of wafer rotation, admixture solvents a kind of or two kinds in propylene glycol monomethyl ether, acetate propylene glycol methyl esters, OK73 diluent, cyclohexanone and the gamma-butyrolacton are sprayed on crystal column surface, simultaneously organic contamination that produces in film deposition process before the crystal column surface lithographic process and the ammonia pollution that produces in the photoetching district are cleaned;
Second step: the described solvent of removing crystal column surface by the rotation of wafer.
5. the cleaning method of crystal column surface according to claim 4, it is characterized in that: described OK73 diluent, it is the mixture of single ethylether propylene glycol and propylene glycol methyl ether acetate, the mass percent of wherein single ethylether propylene glycol is 70%, and the mass percent of propylene glycol methyl ether acetate is 30%.
6. the cleaning method of crystal column surface according to claim 4, the consumption that it is characterized in that described solvent is 15ml～30ml.
7. the cleaning method of crystal column surface according to claim 4 is characterized in that: wafer carries out the solvent spraying in the first step under the situation of rotation, and the rotary speed of wafer is 100～5000rpm, and spraying and scavenging period are 5～50 seconds.
8. the cleaning method of crystal column surface according to claim 7 is characterized in that: the rotary speed of wafer is between 2000～3000rpm in the first step, and spraying and time of cleaning were at 10～20 seconds.
9. the cleaning method of crystal column surface according to claim 4 is characterized in that: remove described solvent by the wafer rotation in second step, the rotary speed of wafer is 100～5000rpm, and the time is 5～50 seconds.
10. the cleaning method of crystal column surface according to claim 9 is characterized in that: the rotary speed of wafer is between 2000～3000rpm in second step, and the time is 10～20 seconds.
11. the application of the cleaning reagent that organic contamination that a kind of or two kinds of admixture solvents in the described propylene glycol monomethyl ether of claim 1, acetate propylene glycol methyl esters, OK73 diluent, cyclohexanone and the gamma-butyrolacton produce in film deposition process before as the crystal column surface lithographic process and the ammonia that produces in the photoetching district pollute.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100267573A CN100459057C (en) | 2006-05-22 | 2006-05-22 | Cleaning method of crystal column surface |
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|---|---|---|---|
| CNB2006100267573A CN100459057C (en) | 2006-05-22 | 2006-05-22 | Cleaning method of crystal column surface |
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| CN100459057C true CN100459057C (en) | 2009-02-04 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108345176A (en) * | 2018-03-02 | 2018-07-31 | 睿力集成电路有限公司 | Photoresist coating process, wetting solvents screening technique and wetting solvents |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102375342A (en) * | 2010-08-24 | 2012-03-14 | 中芯国际集成电路制造(上海)有限公司 | Coating method of photoresist |
| CN103367107B (en) * | 2012-04-09 | 2016-04-20 | 中芯国际集成电路制造(上海)有限公司 | Improve the method for surface conjunction power |
| CN105573068B (en) * | 2014-10-10 | 2019-11-05 | 中芯国际集成电路制造(上海)有限公司 | The reworking method of photoresist minimizing technology and photoetching process |
| CN111146073B (en) * | 2018-11-05 | 2022-03-22 | 北京北方华创微电子装备有限公司 | Cleaning method and cleaning apparatus |
| JP2024503164A (en) * | 2020-08-11 | 2024-01-25 | 株式会社レゾナック | solvent composition |
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| US4983490A (en) * | 1985-10-28 | 1991-01-08 | Hoechst Celanese Corporation | Photoresist treating composition consisting of a mixture of propylene glycol alkyl ether and propylene glycol alkyl ether acetate |
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