CN102915908A - Pretreatment method for silanization and silanization method comprising the method - Google Patents
Pretreatment method for silanization and silanization method comprising the method Download PDFInfo
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- CN102915908A CN102915908A CN2011102198193A CN201110219819A CN102915908A CN 102915908 A CN102915908 A CN 102915908A CN 2011102198193 A CN2011102198193 A CN 2011102198193A CN 201110219819 A CN201110219819 A CN 201110219819A CN 102915908 A CN102915908 A CN 102915908A
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- silylation
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Abstract
The invention relates to a pretreatment method for silanization, which is characterized in before performing silanization to a wafer, performing the following steps: heating the wafer, and introducing nitrogen to purge; introducing diluted silanization agent gas; and introducing the nitrogen to purge continuously, and exhausting the gas. The invention further relates to a silanization method comprising the pretreatment 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 has 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, will certainly cause the poor adhesion of photoresist and wafer, even causing local gap or bubble, gluing thickness and uniformity all have been subject to impact, thereby have affected lithographic results and development.
In order to address this problem, introduced the silylation operation in the coating technique, by hydrogen bond, hydroxyl or carboxyl and silylation agent reaction, form silicon oxide layer at wafer, thereby wafer surface is become hydrophobicity by hydrophily, hydrophobic group can be combined with photoresist well, play the effect of coupling, moreover, in the process of developing, because it has strengthened the adhesion of photoresist and wafer, thereby effectively suppresses the side direction etching that etching liquid enters mask and wafer.Silylation agent commonly used, hexamethyldisiloxane (Hexamethyldisilazane, HMDS) for example, be coated onto wafer surface after, can react the compound that generates take siloxanes as main body by heating, make wafer surface become hydrophobicity by hydrophily.
Yet if silylation agent and wafer surface can not homogeneous reactions, perhaps process cavity or wafer surface have particulate, water or chemical residue, and will there be defective in product, such as peel off, particle or bubble etc. in the layer, cause the corrosion-resisting pattern failure.
Summary of the invention
In view of this, need a kind of method that can effectively avoid the corrosion-resisting pattern failure that wafer surface the Harmful Residue (for example water, particulate or chemical residue) causes.
First aspect of the present invention relates to a kind of preprocess method for silylation, it is characterized in that, carries out following steps before wafer is carried out the silylation operation:
With the wafer heating, and logical nitrogen blowing;
Pass into the silylation agent gas of dilution; With
Continue logical nitrogen blowing, and exhaust.
The temperature of heating can be 100 ~ 130 ℃ for heating-up temperature commonly used, considers that the needs of standardized work are preferably 120 ~ 130 ℃.
The flow of nitrogen can be set as required, can for 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 silylation agent gas of dilution, the content of silylation agent gas is 20% ~ 50%, considers that the content of silylation agent gas on the impact of the pre-treatment ability of wafer surface, is preferably 30 ~ 45%.(referring to the percent by volume that silylation agent gas occupies in silylation agent gas and nitrogen or other inert gas mists)
The silylation agent gas of described dilution can be the gaseous mixture of silylation agent gas and other gases.The gas of various other inertia 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 silylation agent gas of dilution can be set as required, can for 100 ml/min (ml/min) to 3000 ml/min (ml/min), consider on the impact of the pre-treatment ability of wafer surface and the cost of existing semicon industry machine, preferably to 1000 ~ 2500 ml/min (ml/min).
The time that each step is carried out is set as required, for example heats and the time of logical nitrogen steps is 3-15 second, is preferably 5 ~ 12 seconds, the time of the silylation agent gas step of logical dilution is 10-25 second, preferred 12 ~ 20 seconds, the time of logical nitrogen and exhaust was 10-20 second, preferred 12 ~ 18 seconds.
The silylation agent can for this area silylation agent commonly used, for example be selected from the group that is comprised of hexamethyldisiloxane, tetramethyl-disilazane, two (dimethylformamide dimethyl base silanes), 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 described preprocess method for silylation in first aspect of the present invention.
The invention provides and a kind ofly between normal silylation operation, carrying out pretreated method.The corrosion-resisting pattern that uses the method can avoid wafer surface water or chemical residue to cause peel off with wafer on air blister defect.Use nitrogen blowing can blow away steam or particulate harmful in the process cavity; The silylation agent gas of dilution can with residual harmful steam reaction, and before implementing the silylation operation process for stabilizing condition; At last, continue logical nitrogen and exhaust, can remove remaining silylation agent gas, and the environment of cleaning process cavity.So, the silylation operation just can reacted under the process cavity environment of the wafer surface of cleaning, stable and cleaning, and then improves the finished product rate.
Description of drawings
Following accompanying drawing of the present invention is used for understanding the present invention at this as a part of 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 processing of the present invention and the comparison diagram of the wafer of processing with prior art, and wherein A is the wafer that general silylation is processed, and B carries out the wafer that silylation is processed afterwards again with the silylation agent preliminary treatment of dilution.
Embodiment
In the following description, a large amount of concrete details have been provided in order to more thorough understanding of the invention is provided.Yet, it will be apparent to one skilled in the art that the present invention can need not one or more these details and implemented.In other example, for fear of obscuring with the present invention, be not described for technical characterictics more well known in the art.
In order thoroughly to understand the present invention; detailed step and structure will be proposed, so that explanation the present invention is the problem that how to solve the corrosion-resisting pattern failure that wafer surface the Harmful Residue in the prior art (for example water, particulate or chemical residue) causes in following description.Obviously, execution of the present invention is not limited to the specific details that the technical staff of semiconductor applications has the knack of.Preferred embodiment of the present invention is described in detail as follows, yet except these were described in detail, the present invention can also have other execution modes.
Take HMDS as example, under normal circumstances, HMDS and the substrate with high surface energy with the OH-group generation chemical reaction of bonding, OH base group modification one-tenth-CH that can substrate surface is all
3Group ,-CH
3Group can become hydrophobicity by hydrophily with the surface, then with photoresist or other organic substances coupling.But except the 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
3Because the silylation operation is to carry out in airtight system, harmful product that reaction generates can be stayed on process cavity and the wafer.Harmful product of staying on the 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.Thereby be highly susceptible to causing the corrosion-resisting pattern defective at wafer.
For addressing the above problem, the present inventor has proposed a kind of new preprocess method that is used for silylation through concentrating on studies, and it is used in before the general silylation operation.
Still take HMDS as example, preprocess method of the present invention comprises: effects on surface has the wafer of water or other chemical residues to heat, and logical nitrogen blowing is removed water vapour or other chemical vaporses with this simultaneously.Pass into the HMDS gas (gaseous mixture of HMDS and nitrogen) of dilution, the steeping in water for reconstitution of HMDS and wafer surface is given birth to reaction and is generated hexa methyl oxy disilicane and NH
3Continue logical nitrogen, the product that these are newly-generated blows away, and discharges by exhaust outlet.Wafer after the preliminary treatment is carried out general silylation with HMDS to be processed.Thereby can with suitable even angle coat photoresist film, make photoresist and wafer reach best bond effect.
Embodiment 1
The system that carries out silylation comprises: heating system, process cavity, silylation agent input port, nitrogen input port, exhaust outlet, vacuum system and control module.
Open heating system, controlled working chamber constant temperature is put into process cavity at 125 ℃ with pending wafer, passes into nitrogen, and the control flow is 10000 ml/min (ml/min).After the 10s, pass into the gaseous mixture of HMDS and nitrogen, the volume ratio of HMDS and nitrogen is: 45:55, and the control flow is after the 15s, stops logical gaseous mixture, continues logical nitrogen, the control flow is 2000 ml/min (ml/min), and from the exhaust outlet exhaust.
Whole process is controlled by control module, and the process cavity temperature keeps constant during the processing.After the preliminary treatment, wafer is carried out general silylation process, the gained wafer is carried out control wafer worsen experiment test (control wafer worse test), compare with the wafer that has only carried out general silylation processing.
Control wafer worsens experiment test and carries out in such a way:
The Surfscan series of wafers defective and the Surface Quality Inspection System Surfscan SPx that use KLA-Tencor to produce detect wafer surface.The gained image is two pictures on Fig. 1 top.
The SEMVision of defect recognition SEM system that uses Applied Materials to produce detects wafer.The gained image is three photos of Fig. 1 bottom.
Result relatively as shown in Figure 1.Can find out, use preprocess method of the present invention that wafer surface blemish after silylation is processed is obviously reduced.
Comparative example 1
Use the experiment condition identical with embodiment 1, difference is that the stage that passes into gaseous mixture at embodiment 1 only leads to nitrogen.
The gained wafer is through control wafer test (control wafer), and is similar to the wafer that only carries out general silylation processing.This be because the water of wafer surface or organic residue since with hydrogen bond or the hydroxyl bonding of wafer surface, be liquid state under the working temperature of process cavity, only use nitrogen blowing to be removed.Therefore, when follow-up silylation is processed, still with HMDS steam generation reaction, cause wafer surface blemish.
In sum, the invention provides and a kind ofly between normal silylation operation, carrying out pretreated method.The corrosion-resisting pattern that uses the method can avoid wafer surface water or chemical residue to cause peel off with wafer on air blister defect.Use nitrogen blowing can blow away steam or particulate harmful in the process cavity; The silylation agent gas of dilution can with residual harmful steam reaction, and before implementing the silylation operation process for stabilizing condition; At last, continue logical nitrogen and exhaust, can remove remaining silylation agent gas, and the environment of cleaning process cavity.So, the silylation operation just can reacted under the process cavity environment of the wafer surface of cleaning, stable and cleaning, and then improves the finished product rate.
And three steps of preprocess method of the present invention are the schemes that a cover is integrated, and do not need mobile wafer, and can directly 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 is used for for example and the purpose of explanation, but not is intended to the present invention is limited in the described scope of embodiments.It will be appreciated by persons skilled in the art that in addition the present invention is not limited to above-described embodiment, can also make more kinds of variants and modifications according to instruction of the present invention, these variants and modifications all drop in the present invention's scope required for protection.Protection scope of the present invention is defined by the appended claims and equivalent scope thereof.
Claims (14)
1. a preprocess method that is used for silylation is characterized in that, carries out following steps before wafer is carried out the silylation operation:
With the wafer heating, and logical nitrogen blowing;
Pass into the silylation agent gas of dilution; With
Continue logical nitrogen blowing, and exhaust.
2. the method for claim 1 is characterized in that, in the silylation agent gas of described dilution, the content of silylation agent gas is 20 ~ 50vol%.
3. method as claimed in claim 2 is characterized in that, in the silylation agent gas of described dilution, the content of silylation agent gas is 30 ~ 45vol%.
4. the method for claim 1 is characterized in that, the silylation agent gas of described dilution is the gaseous mixture of silylation agent gas and other gases.
5. method as claimed in claim 4 is characterized in that, described other gases are nitrogen, rare gas or their combination.
6. the method for claim 1, it is characterized in that, described silylation agent is selected from the group that is comprised of hexamethyldisiloxane, tetramethyl-disilazane, two (dimethylformamide dimethyl base silanes), 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 silylation agent gas of described dilution is that 100 ml/min are to 3000 ml/min.
9. method as claimed in claim 8 is characterized in that, the flow of the silylation agent gas of described dilution is that 1000 ml/min are to 2500 ml/min.
10. the method for claim 1 is characterized in that, the temperature of described heating is 100 ~ 130 ℃.
11. the method for claim 1 is characterized in that, the time of heating and logical nitrogen steps is 3-15 second.
12. the method for claim 1 is characterized in that, the time of the silylation agent gas step of logical dilution is 10-25 second.
13. the method for claim 1 is characterized in that, the time of logical nitrogen and exhaust is 10-20 second.
14. a silylation methods, it comprises each described preprocess method of claim 1 ~ 13.
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| CN201110219819.3A CN102915908B (en) | 2011-08-03 | 2011-08-03 | For silylation preprocess method and comprise the silylation methods of the method |
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Cited By (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 |
| CN109962026A (en) * | 2017-12-26 | 2019-07-02 | 无锡华润上华科技有限公司 | A kind of preprocess method and photolithography method of wafer |
Citations (3)
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|---|---|---|---|---|
| JPH05251324A (en) * | 1991-11-13 | 1993-09-28 | Nec Corp | Surface treatment apparatus of semiconductor substrate |
| 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 |
-
2011
- 2011-08-03 CN CN201110219819.3A patent/CN102915908B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05251324A (en) * | 1991-11-13 | 1993-09-28 | Nec Corp | Surface treatment apparatus of semiconductor substrate |
| 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 |
|---|
| 庞克俭: "HMDS预处理系统", 《电子工业专用设备》, no. 10, 31 October 2006 (2006-10-31), pages 70 - 72 * |
Cited By (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 |
| CN109962026A (en) * | 2017-12-26 | 2019-07-02 | 无锡华润上华科技有限公司 | A kind of preprocess method and photolithography method of wafer |
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| CN102915908B (en) | 2016-02-17 |
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