CN102915908B - For silylation preprocess method and comprise the silylation methods of the method - Google Patents
For silylation preprocess method and comprise the silylation methods of the method Download PDFInfo
- Publication number
- CN102915908B CN102915908B CN201110219819.3A CN201110219819A CN102915908B CN 102915908 B CN102915908 B CN 102915908B CN 201110219819 A CN201110219819 A CN 201110219819A CN 102915908 B CN102915908 B CN 102915908B
- Authority
- CN
- China
- Prior art keywords
- monosilane
- silylation
- oxidant gas
- wafer
- dilution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Formation Of Insulating Films (AREA)
- Exposure Of Semiconductors, Excluding Electron Or Ion Beam Exposure (AREA)
Abstract
The present invention relates to a kind of preprocess method for silylation, it is characterized in that, before silylation operation is carried out to wafer, carry out following steps: wafer is heated, and logical nitrogen purges; Pass into the monosilane oxidant gas of dilution; Purge with the logical nitrogen of continuation, and be vented.The invention still further relates to a kind of silylation methods comprising this preprocess method.
Description
Technical field
The present invention relates to technical field of manufacturing semiconductors, particularly a kind of preprocess method for silylation.
Background technology
In production process of semiconductor, photoetching is a vital process procedure, and the quality of coating technique, directly have influence on the quality of photoetching.In coating technique, the used photoresist overwhelming majority is hydrophobic, and the hydrogen bond of wafer surface, hydroxyl or carboxyl and residual hydrone are hydrophilic, if at the direct gluing of wafer surface, the poor adhesion of photoresist and wafer will certainly be caused, even cause gap or the bubble of local, rubberization thickness and uniformity all receive impact, thus have impact on lithographic results and development.
In order to address this problem, silylation operation is introduced in coating technique, reacted by hydrogen bond, hydroxyl or carboxyl and monosilane agent, wafer forms silicon oxide layer, thus wafer surface is become hydrophobicity from hydrophily, hydrophobic group can be combined with photoresist well, play the effect of coupling, moreover, in the process of development, owing to it enhancing the adhesion of photoresist and wafer, thus the side direction effectively suppressing etching liquid to enter mask and wafer etches.Conventional monosilane agent, such as hexamethyldisiloxane (Hexamethyldisilazane, HMDS), after being coated onto wafer surface, can reacting the compound generated based on siloxanes, making wafer surface become hydrophobicity from hydrophily by heating.
But if monosilane agent and wafer surface can not homogeneous reactions, or process cavity or wafer surface have particulate, water or chemical residue, then product is by existing defects, such as, to peel off, particle or bubble etc. in layer, cause corrosion-resisting pattern failure.
Summary of the invention
In view of this, the method for the corrosion-resisting pattern failure needing one can effectively avoid wafer surface the Harmful Residue (such as water, particulate or chemical residue) to cause.
First aspect of the present invention relates to a kind of preprocess method for silylation, it is characterized in that, before carrying out silylation operation to wafer, carry out following steps:
Wafer is heated, and logical nitrogen purges;
Pass into the monosilane oxidant gas of dilution; With
Continue logical nitrogen to purge, and be vented.
The temperature of heating is conventional heating-up temperature, can be 100 ~ 130 DEG C, and that considers standardized work needs preferably 120 ~ 130 DEG C.
The flow of nitrogen can set as required, can be 7000 ml/min (ml/min) to 12000 ml/min (ml/min), consider the needs of standardized work, be preferably 9000 ~ 11000 ml/min (ml/min).
In the monosilane oxidant gas of dilution, the content of monosilane oxidant gas is 20% ~ 50%, considers the impact of the content of monosilane oxidant gas on the pre-treatment ability of wafer surface, is preferably 30 ~ 45%.(referring to the percent by volume that in monosilane oxidant gas and nitrogen or other inert gas mists, monosilane oxidant gas occupies)
The monosilane oxidant gas of described dilution can be the gaseous mixture of silylation agent gas and other gases.The gas of other inertia various can use, as long as this gas can not produce side reaction to silylation.The gas that preferably can be used for mixing is nitrogen or rare gas or their combination.Consider cost and convenience, most preferably use nitrogen.
The flow of the monosilane oxidant gas of dilution can set as required, can be that 100 ml/min (ml/min) are to 3000 ml/min (ml/min), consider the cost of impact on the pre-treatment ability of wafer surface and existing semicon industry machine, preferably to 1000 ~ 2500 ml/min (ml/min).
The time that each step is carried out sets as required, such as, heat and the time of leading to nitrogen steps is 3-15 second, is preferably 5 ~ 12 seconds, the time of the monosilane agent gas step of logical dilution is 10-25 second, preferably 12 ~ 20 seconds, the time that logical nitrogen is also vented was 10-20 second, preferably 12 ~ 18 seconds.
The monosilane agent that monosilane agent can be commonly used for this area, such as, be selected from the group be made up of hexamethyldisiloxane, tetramethyl-disilazane, two (dimethylformamide dimethyl base silane), two (dimethylaminomethyl silane), dimetylsilyl dimethylamine, trimethyl silyl dimethylamine, trimethyl silyl diethylamine and dimethylamino pentamethyl silane.Consider cost and the convenience of agents useful for same, be preferably hexamethyldisiloxane.
Second aspect of the present invention relates to a kind of silylation methods, and it comprises the preprocess method for silylation described in the present invention first aspect.
The invention provides one and carry out pretreated method between normal silylation operation.The corrosion-resisting pattern using the method that wafer surface water or chemical residue can be avoided to cause peels off and the air blister defect on wafer.Use nitrogen to purge and can blow away steam harmful in process cavity or particulate; The monosilane oxidant gas of dilution can react with residual dangerous vapors, and before implementing silylation operation process for stabilizing condition; Finally, continue logical nitrogen and be vented, remaining monosilane oxidant gas can be removed, and the environment of clean process cavity.So, silylation operation just can reacted under the wafer surface, stable and clean process cavity environment of cleaning, and then improves finished product rate.
Accompanying drawing explanation
Following accompanying drawing of the present invention in this as a part of the present invention for understanding the present invention.Shown in the drawings of embodiments of the invention and description thereof, be used for explaining principle of the present invention.In the accompanying drawings,
Fig. 1 uses the wafer of method process of the present invention and the comparison diagram with the wafer of prior art process, and wherein A is the wafer of general silylation process, and B carries out the wafer of silylation process again after being the monosilane agent preliminary treatment with dilution.
Embodiment
In the following description, a large amount of concrete details is given to provide more thorough understanding of the invention.But, it will be apparent to one skilled in the art that the present invention can be implemented without the need to these details one or more.In other example, in order to avoid obscuring with the present invention, technical characteristics more well known in the art are not described.
In order to thoroughly understand the present invention; by in following description, detailed step and structure are proposed, to illustrate that the present invention is the problem how solving the corrosion-resisting pattern failure that wafer surface the Harmful Residue in prior art (such as water, particulate or chemical residue) causes.Obviously, the specific details that the technical staff that execution of the present invention is not limited to semiconductor applications has the knack of.Preferred embodiment of the present invention is described in detail as follows, but except these are described in detail, the present invention can also have other execution modes.
For HMDS, under normal circumstances, HMDS and the substrate with high surface energy with the OH-group generation chemical reaction of bonding, can by OH base group modification one-tenth-CH all for substrate surface
3group ,-CH
3surface can be become hydrophobicity from hydrophily by group, then mates with photoresist or other organic substances.But except OH-group, substrate surface also has the chemical residue of water or pre-epitaxial loayer (pre-layer), and its steam can mix with HMDS, and reaction generates hexa methyl oxy disilicane and NH
3.Because silylation operation is carried out in airtight system, the noxious products that reaction generates can be stayed on process cavity and wafer.The noxious products stayed on wafer can affect the bond effect of photoresist film and wafer in the operation of follow-up resist coating, and evaporates in follow-up soft baking operation, causes the generation of bubble.Thus be highly susceptible to causing corrosion-resisting pattern defect on wafer.
For solving the problem, the present inventor, through concentrating on studies, proposes a kind of preprocess method for silylation newly, before it is used in general silylation operation.
Still for HMDS, preprocess method of the present invention comprises: effects on surface has the wafer of water or other chemical residues to heat, and logical nitrogen purges simultaneously, removes water vapour or other chemical vaporses with this.Pass into the HMDS gas (gaseous mixture of HMDS and nitrogen) of dilution, the water of HMDS and wafer surface reacts and generates hexa methyl oxy disilicane and NH
3.Continue logical nitrogen, the product that these are newly-generated blows away, and is discharged by exhaust outlet.General silylation process is carried out to the wafer HMDS after preliminary treatment.Thus photoresist film can be coated with suitable even angle, make the bond effect that photoresist and wafer reach best.
Embodiment 1
The system of carrying out silylation comprises: heating system, process cavity, monosilane agent input port, nitrogen inlet, exhaust outlet, vacuum system and control module.
Open heating system, pending wafer, at 125 DEG C, is put into process cavity, is passed into nitrogen by controlled working chambers constant, and controlling flow is 10000 ml/min (ml/min).After 10s, pass into the gaseous mixture of HMDS and nitrogen, the volume ratio of HMDS and nitrogen is: 45:55, and after control flow is 15s, stop logical gaseous mixture, continue logical nitrogen, control flow is 2000 ml/min (ml/min), and from vent.
Whole process is controlled by control module, process cavity temperature remained constant during process.After preliminary treatment, general silylation process is carried out to wafer, control wafer is carried out to gained wafer and worsens experiment test (controlwaferworsetest), compare with the wafer only carrying out general silylation process.
Control wafer worsens experiment test and carries out in such a way:
The Surfscan series of wafers defect using KLA-Tencor to produce and Surface Quality Inspection System SurfscanSPx detect wafer surface.Gained image is two pictures on Fig. 1 top.
The defect recognition SEM system SEMVision using AppliedMaterials to produce detects wafer.Gained image is three photos of Fig. 1 bottom.
Result relatively as shown in Figure 1.Can find out, the wafer surface blemish after using preprocess method of the present invention to make silylation process obviously reduces.
Comparative example 1
Use the experiment condition identical with embodiment 1, difference is the stage only logical nitrogen passing into gaseous mixture in embodiment 1.
Gained wafer is through control wafer test (controlwafer), similar to the wafer only carrying out general silylation process.This is because the water of wafer surface or organic residue are due to the hydrogen bond or hydroxyl bonding with wafer surface, be liquid under the working temperature of process cavity, only using nitrogen to purge cannot be removed.Therefore, when follow-up silylation process, still react with HMDS steam generation, cause wafer surface blemish.
In sum, the invention provides one and carry out pretreated method between normal silylation operation.The corrosion-resisting pattern using the method that wafer surface water or chemical residue can be avoided to cause peels off and the air blister defect on wafer.Use nitrogen to purge and can blow away steam harmful in process cavity or particulate; The monosilane oxidant gas of dilution can react with residual dangerous vapors, and before implementing silylation operation process for stabilizing condition; Finally, continue logical nitrogen and be vented, remaining monosilane oxidant gas can be removed, and the environment of clean process cavity.So, silylation operation just can reacted under the wafer surface, stable and clean process cavity environment of cleaning, and then improves finished product rate.
And three steps of preprocess method of the present invention are the schemes of a set of integration, do not need mobile wafer, and directly can connect follow-up silylation operation, and technique is simple, convenient, and feasibility is high.
The present invention is illustrated by above-described embodiment, but should be understood that, above-described embodiment just for the object of illustrating and illustrate, and is not intended to the present invention to be limited in described scope of embodiments.In addition it will be appreciated by persons skilled in the art that the present invention is not limited to above-described embodiment, more kinds of variants and modifications can also be made according to instruction of the present invention, within these variants and modifications all drop on the present invention's scope required for protection.Protection scope of the present invention defined by the appended claims and equivalent scope thereof.
Claims (13)
1. for a preprocess method for silylation, it is characterized in that, before silylation operation is carried out to wafer, carry out following steps:
Heated by wafer, and logical nitrogen purges, wherein, the temperature of described heating is 100 ~ 130 DEG C;
Pass into the monosilane oxidant gas of dilution; With
Continue logical nitrogen to purge, and be vented.
2. the method for claim 1, is characterized in that, in the monosilane oxidant gas of described dilution, the content of monosilane oxidant gas is 20 ~ 50vol%.
3. method as claimed in claim 2, it is characterized in that, in the monosilane oxidant gas of described dilution, the content of monosilane oxidant gas is 30 ~ 45vol%.
4. the method for claim 1, is characterized in that, the monosilane oxidant gas of described dilution is the gaseous mixture of monosilane oxidant gas and other gases.
5. method as claimed in claim 4, it is characterized in that, other gases described are nitrogen, rare gas or their combination.
6. the method for claim 1, it is characterized in that, described monosilane agent is selected from the group be made up of hexamethyldisiloxane, tetramethyl-disilazane, two (dimethylformamide dimethyl base silane), two (dimethylaminomethyl silane), dimetylsilyl dimethylamine, trimethyl silyl dimethylamine, trimethyl silyl diethylamine and dimethylamino pentamethyl silane.
7. the method for claim 1, is characterized in that, the flow of described nitrogen is that 7000 ml/min are to 12000 ml/min.
8. the method for claim 1, is characterized in that, the flow of the monosilane oxidant gas of described dilution is that 100 ml/min are to 3000 ml/min.
9. method as claimed in claim 8, it is characterized in that, the flow of the monosilane oxidant gas of described dilution is that 1000 ml/min are to 2500 ml/min.
10. the method for claim 1, is characterized in that, heats and the time of leading to nitrogen steps is 3-15 second.
11. the method for claim 1, is characterized in that, the time of the monosilane agent gas step of logical dilution is 10-25 second.
12. the method for claim 1, is characterized in that, the time that logical nitrogen is also vented is 10-20 second.
13. 1 kinds of silylation methods, it comprises the preprocess method described in any one of claim 1 ~ 12.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110219819.3A CN102915908B (en) | 2011-08-03 | 2011-08-03 | For silylation preprocess method and comprise the silylation methods of the method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110219819.3A CN102915908B (en) | 2011-08-03 | 2011-08-03 | For silylation preprocess method and comprise the silylation methods of the method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102915908A CN102915908A (en) | 2013-02-06 |
| CN102915908B true CN102915908B (en) | 2016-02-17 |
Family
ID=47614231
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110219819.3A Active CN102915908B (en) | 2011-08-03 | 2011-08-03 | For silylation preprocess method and comprise the silylation methods of the method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102915908B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106757371A (en) * | 2016-12-19 | 2017-05-31 | 山东大学 | A kind of organo-mineral complexing perovskite monocrystalline induced conversion method and device based on methylamine atmosphere |
| CN109962026B (en) * | 2017-12-26 | 2022-04-19 | 无锡华润上华科技有限公司 | Pretreatment method and photoetching method of wafer |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1166798A (en) * | 1994-11-22 | 1997-12-03 | 配合液系统公司 | Non-aminic photoresist adhesion promoters for microelectronic applications |
| CN101388329A (en) * | 2008-10-30 | 2009-03-18 | 无锡华润上华科技有限公司 | Method for eliminating aqueous vapor on chip surface |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3074858B2 (en) * | 1991-11-13 | 2000-08-07 | 日本電気株式会社 | Semiconductor substrate surface treatment apparatus and surface treatment method |
-
2011
- 2011-08-03 CN CN201110219819.3A patent/CN102915908B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1166798A (en) * | 1994-11-22 | 1997-12-03 | 配合液系统公司 | Non-aminic photoresist adhesion promoters for microelectronic applications |
| CN101388329A (en) * | 2008-10-30 | 2009-03-18 | 无锡华润上华科技有限公司 | Method for eliminating aqueous vapor on chip surface |
Non-Patent Citations (1)
| Title |
|---|
| HMDS预处理系统;庞克俭;《电子工业专用设备》;20061031(第10期);第70-72页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102915908A (en) | 2013-02-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR101911469B1 (en) | Silicon nitride passivation layer for covering high aspect ratio features | |
| CN105144420B (en) | For processing the method for OLED device | |
| CN1837404B (en) | Film-forming apparatus and film-forming method | |
| US9090782B2 (en) | Liquid chemical for forming water repellent protective film | |
| KR20190049893A (en) | Low Temperature Formation of High-Quality Silicon Oxide Films in Semiconductor Device Manufacturing | |
| KR101363441B1 (en) | Chemical solution for formation of protective film, process for preparing thereof and process for cleaning using the same | |
| CN105143121A (en) | Facilitated processing for controlling bonding between sheet and carrier | |
| JP2017034245A (en) | Method for integrating halide-containing ald film on sensitive materials | |
| US7954452B2 (en) | Film formation apparatus for semiconductor process and method for using the same | |
| KR20100128302A (en) | Process sequence for formation of patterned hard mask film (rfp) without need for photoresist or dry etch | |
| JP2011014906A (en) | Method and apparatus for processing substrate | |
| JP2007214513A (en) | Substrate processing apparatus, substrate processing method, and storage medium | |
| US20210384029A1 (en) | Modifying hydrophobicity of a wafer surface using an organosilicon precursor | |
| JP2009141329A (en) | Plasma surface treatment for preventing pattern collapse in liquid immersion photolithography | |
| CN104916576B (en) | Process, wash chamber and the plasma processing device of aluminum interconnection layer | |
| CN108352309B (en) | Substrate processing method and substrate processing apparatus | |
| WO2009099713A2 (en) | Elimination of photoresist material collapse and poisoning in 45-nm feature size using dry or immersion lithography | |
| US7691445B2 (en) | Film formation apparatus and method of using the same | |
| KR101139078B1 (en) | Film formation apparatus and method for using the same, and computer readable medium | |
| CN102915908B (en) | For silylation preprocess method and comprise the silylation methods of the method | |
| JP2012044065A (en) | Method for processing substrate and apparatus for processing substrate | |
| TW200818291A (en) | Substrate processing method and substrate processing apparatus | |
| JP5248652B2 (en) | Substrate processing method and substrate processing apparatus | |
| US20110174337A1 (en) | Method and apparatus for recovering pattern on silicon substrate | |
| US20130146100A1 (en) | Water Repellent Protective Film Forming Agent, Liquid Chemical for Forming Water Repellent Protective Film, and Wafer Cleaning Method Using Liquid Chemical |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |