CN102569023B - A kind of cleaning method reducing metal erosion - Google Patents
A kind of cleaning method reducing metal erosion Download PDFInfo
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- CN102569023B CN102569023B CN201010620024.9A CN201010620024A CN102569023B CN 102569023 B CN102569023 B CN 102569023B CN 201010620024 A CN201010620024 A CN 201010620024A CN 102569023 B CN102569023 B CN 102569023B
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Abstract
The invention discloses a kind of cleaning method reducing metal level corrosion.In present invention deionized water rinse cycle after etching remnants has been cleaned, add oxidant.The rinse method of the present invention may utilize the character of the surface passivation of aluminum, defines one layer of dense oxidation film on the surface of aluminum, effectively reduces the generation of corrosion.
Description
Technical field
The present invention relates to a kind of cleaning method reducing metal level corrosion, it is more particularly related to
A kind of reduce after quasiconductor aluminum metal layer etching the cleaning method of aluminum corrosion in cleaning process.
Background technology
In semiconductor fabrication, produce after more and more removing metal level etching with fluorine-containing cleaning solution
Residue, cleaned the sidewall of rear metal and easily produced various corrosion with surface.
In common semiconductor fabrication process, by the dielectric layer on wafer, such as silicon dioxide, nitrogen
SiClx and low-k materials etc. or conductive layer such as Al (aluminum), resist coating on the surface such as Cu (copper), exposure
After development, then utilize plasma dry etch that circuit pattern is shifted corresponding conductive layer or dielectric layer
On.The side wall passivation protective layer produced when photoresist after etching and being ashed is remaining and etches, utilization
Organic cleaning fluid removes.After producing at present the upper etching used, cleanout fluid mainly has two classes, one be with
Azanol is the cleanout fluid of main active ingredient, such as EKC265, EKC270, EKC270T, ACT935,
ACT940 etc., the another kind of cleanout fluid such as IDEAL Clean being mainly with F ion as active component
960, IDEAL Clean 815, ST-250 etc..
In order to reduce the electromigration of aluminum steel, the metallic aluminium in semiconductor crystal wafer typically contains 1～3wt%
Copper.If copper is skewness in physical vapor deposition process, the core of copper segregation can be formed.
These cores are easy in cleaning process the aluminum to surrounding and form stream galvano-cautery.Two based cleaning liquids are cleaned
After aluminum steel be likely to occur stream galvano-cautery.
In addition to stream galvano-cautery, it is also possible to there are some other corrosion conditions on metal wire.Chlorine, fluorine
Can cause corrosion in a humidity environment etc. anion, form aluminium hydroxide, reaction can persistently be carried out, instead
After answering product to be cleaned out, the biggest hole can be formed.
At the grain boundary of aluminum metal, the weakest, it is easily subject to the attack of cleanout fluid and water, is formed very
Coarse surface.
In order to reduce the attack to metal wire, technique bar can be improved the most traditionally in terms of three
Part.
The first be the etching from aluminum metal layer and ashing link set about, such as following patent:
US5545289A podzolic process after having etched introduces oxygen (O2), containing amine gas
((Rx3)-N, steam (H2And fluoro-gas (CH O),XFY) formed blunt at the sidewall of metal wire
Change protective layer, reduce corrosion and stream galvano-cautery that chlorine causes.The etch-protecting layer formed after ashing is connecing
The wet method got off goes also to be intended in the link that etching is remaining to remove, and the interface of aluminum bronze still can be exposed to electricity
In the environment of electrolyte solution, so the effect for anti-fluid stopping galvano-cautery is limited.
First US5946589 is to utilize after etching during ashing, in the cavity of ashing 230～
Under the conditions of 250 DEG C, it is passed through oxygen, makes the surface of aluminum form one layer 400～800A oxide film,
To protect aluminum, then the water of rinsing is reduced to 5～10 DEG C, reduces the speed of stream galvano-cautery.Use oxygen
Gas is passivated the effect on the surface of aluminum should be very poor, because the surface of aluminum is wrapped by fine and close Etch Passivation
Wrap up in, reduce the temperature of washings, should have certain effect in theory.
The second is to use the little solvent of degree of ionization instead to remove the remnants after etching, such as following patent:
US6274504B2 utilizes the neat solvent (NMP) of 65～85 DEG C and 20～40 DEG C directly to clean quarter
Remnants after erosion prevent corrosion, because not having the environment of electrolyte, the effect reducing corrosion is preferable, but
Neat solvent does not has active component, the remnants that inorganic content is higher are difficult to remove totally.
The third is to utilize to have the metal coating working solution of special formulation to protect aluminum metal not to be corroded,
Such as following patent:
US6156661 Yu US5981454 is by one containing azanol, organic acid, ammonia, and pH buffering is molten
The organic solvent that the metal protection liquid of liquid is used when cleaning after replacing etching, or it is used as CMP cleaning
After the abluent of minimizing defect.This way can effectively reduce corrosion of metal degree, simply exists
The substantial amounts of metal protection liquid that application needs, because the character of this liquid can bring rinse bath into along with crystal column surface
The quantity of interior cleanout fluid changes rapidly.
In sum, in the prior art, it is not fully solved in semiconductor fabrication process, especially
It it is the metal erosion problem not solving easily to produce when cleaning after aluminum metal layer etches.
Summary of the invention
Problem to be solved by this invention is: provides a kind of deionized water cleaning method, is effectively reduced half
After conductor aluminum metal layer etching, the aluminum corrosion produced when cleaning by etch residue.
Technical scheme is as follows: etching the deionized water drift after remaining cleaned liquid has cleaned
During washing, the deionized water of slot type chemical cleaning tank adds oxidant.
In the present invention, preferably rinsing condition is:
A. in de-ionized water tank 1, clean 30s～5min；
B. in de-ionized water tank 2, add the hydrogen peroxide of 0.01～5wt%, clean 1～10min.
In the present invention, cleanout fluid optional IDEAL Clean 960, IDEAL Clean 815, ST-250,
EKC265, EKC270, EKC270T, ACT935 or ACT940.
In the present invention, oxidant is hydrogen peroxide, utilizes the character of the surface passivation of aluminum, in the surface shape of aluminum
Become one layer of dense oxidation film, be effectively reduced the generation of corrosion.Ozone can also reach same effect
Really, but oxidisability is the strongest, it is not easy to control.
The positive effect of the present invention is: after the metal level remnants after utilizing etching, utilize go from
During sub-water rinsing wafer, add appropriate oxidant in deionized water, in the metal surface of aluminum
Form one layer of fine and close oxide-film, reduce the corrosion of metal surface.
Accompanying drawing illustrates:
Fig. 1 is the electromicroscopic photograph after prior art is cleaned；
Fig. 2 is the electromicroscopic photograph after placing 48 hours after prior art is cleaned；
Fig. 3 is the electromicroscopic photograph after one embodiment of the invention is cleaned；
Fig. 4 is the electromicroscopic photograph after placing 48 hours after one embodiment of the invention is cleaned；
Fig. 5 is the electromicroscopic photograph after another embodiment of the present invention is cleaned；
Fig. 6 is the electromicroscopic photograph after placing 48 hours after another embodiment of the present invention is cleaned；
Fig. 7 is the electromicroscopic photograph after another embodiment of the present invention is cleaned；
Fig. 8 is the electromicroscopic photograph after placing 48 hours after another embodiment of the present invention is cleaned；
Fig. 9 is the electromicroscopic photograph after another embodiment of the present invention is cleaned；
Figure 10 is the electromicroscopic photograph after placing 48 hours after another embodiment of the present invention is cleaned.
Detailed description of the invention
Further illustrate the present invention below by the mode of embodiment, but the most therefore limit the present invention to
Among described scope of embodiments.
Embodiment 1～4
Table 1 gives embodiments of the invention 1～4 and comparative example 1, uses commercially available fluorine-containing cleaning solution
After IDEAL Clean 960 cleans the wafer after aluminum metal layer has etched, utilize the experiment in following table
Scheme rinses.
Table 1
Effect example
After each cleaning program of table 1 rinses, utilize identical rotation to dry program and be dried wafer, finally
The surface stream galvano-cautery situation of aluminum metal pattern on wafer is checked with scanning electron microscope.The result of electromicroscopic photograph
As shown in drawings.
Comparative example 1 in table 1, takes normal wash flow process, is added without oxidant.Its wash result is such as
Shown in Fig. 1 and Fig. 2, when wafer cleans after aluminum metal layer etching, copper segregation district produces stream galvano-cautery, and
And surface roughness, place 48 hours and can become more serious with post-etching, and become more in quantity,
Heavy corrosion can be added under the effect of the aluminum side wall steam in atmosphere that this explanation is passivated the most completely, on the one hand be
Because the reason of aluminum institute cupric, on the other hand it is probably in aluminum contained fluorine and chlorine element under steam effect
Cause corrosion.
Embodiment 1～4 in table 1, with the addition of the hydrogen peroxide of different proportion in deionized water rinse cycle
Do oxidant.For the corrosion of metallic aluminium sidewall, improve significantly.The cleaning knot of embodiment 1 correspondence
Really electromicroscopic photograph is Fig. 3, Fig. 4, does not flow the hole of galvano-cautery, and sidewall is the most coarse, mainly because of
Concentration for hydrogen peroxide is low, and passivation ability is weak；The time that the first step is cleaned is short, result in and remains more quarters
Cleanout fluid after erosion is on the surface of aluminum, and the surface microstructure interface making aluminum is under attack, thus rougher, separately
The most weak oxidability also makes the passivating film defective tightness on surface.The wash result Electronic Speculum of embodiment 3 correspondence
Photo is Fig. 7, Fig. 8, and display sidewall surfaces does not has hole, but relatively rough, is because the first step
The time cleaned is longer, and degree now under attack between the crystal grain boundary of the sidewall of aluminum is relatively deep,
Becoming coarse, next step oxidation is cleaned and is not helped coarse surface.The cleaning of embodiment 2
Result electromicroscopic photograph is Fig. 5, Fig. 6, and the wash result electromicroscopic photograph of embodiment 4 is Fig. 9, Figure 10.
Electromicroscopic photograph result sidewall after cleaning with the cleaning program of embodiment 2 and embodiment 4 is smooth, does not has corruption
Erosion, so embodiment 2 and embodiment 4 are preferably scavenging period and the combination of oxidant concentration.
Being shown by data above and accompanying drawing, the cleaning method of the present invention has the advantage that
After aluminum metal layer remnants after utilizing etching, utilize effective added with the deionized water of oxidant
The corrosion decreasing aluminum metal surface.
The present invention can summarize with other the concrete form without prejudice to the spirit or essential characteristics of the present invention.
Therefore, no matter from the point of view of which, the embodiment above of the present invention all can only be considered saying the present invention
Bright and can not limit the present invention, claims indicate the scope of the present invention, and above-mentioned explanation is not
Point out the scope of the present invention, therefore, in being implication that claims of the present invention is suitable and scope
Any change, is all considered as being included within the scope of the claims.
Claims (2)
1. reducing a cleaning method for metal level corrosion, the metal level after etching is at cleaned liquid
After etching remnants is cleaned, rinse through deionized water, it is characterised in that:
The first step: clean 30s～5min in de-ionized water tank 1；
Second step: in de-ionized water tank 2, adds the hydrogen peroxide of 0.01～5wt%, cleans
After 1～10min, cleaning terminates.
2. cleaning method as claimed in claim 1, it is characterised in that: described cleanout fluid is
IDEAL Clean 960, IDEAL Clean 815, ST-250, EKC265, EKC270,
EKC270T, ACT935 or ACT940.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010620024.9A CN102569023B (en) | 2010-12-30 | 2010-12-30 | A kind of cleaning method reducing metal erosion |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010620024.9A CN102569023B (en) | 2010-12-30 | 2010-12-30 | A kind of cleaning method reducing metal erosion |
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| CN102569023A CN102569023A (en) | 2012-07-11 |
| CN102569023B true CN102569023B (en) | 2016-09-14 |
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Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104810267B (en) * | 2014-01-28 | 2018-07-10 | 中芯国际集成电路制造(上海)有限公司 | The forming method of metal gates |
| TWI816502B (en) * | 2022-04-21 | 2023-09-21 | 陳嘉朗 | Cleaning equipment |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5453401A (en) * | 1991-05-01 | 1995-09-26 | Motorola, Inc. | Method for reducing corrosion of a metal surface containing at least aluminum and copper |
| US5911836A (en) * | 1996-02-05 | 1999-06-15 | Mitsubishi Gas Chemical Company, Inc. | Method of producing semiconductor device and rinse for cleaning semiconductor device |
| CN1725458A (en) * | 2004-07-22 | 2006-01-25 | 中芯国际集成电路制造(上海)有限公司 | Method for removing lattice defect in pad area of semiconductor device |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3652145B2 (en) * | 1998-11-17 | 2005-05-25 | 茂徳科技股▲フン▼有限公司 | Internal wiring manufacturing method for preventing plug corrosion |
| JP2001217246A (en) * | 2000-02-04 | 2001-08-10 | Toshiba Corp | Semiconductor device and its manufacturing method |
-
2010
- 2010-12-30 CN CN201010620024.9A patent/CN102569023B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5453401A (en) * | 1991-05-01 | 1995-09-26 | Motorola, Inc. | Method for reducing corrosion of a metal surface containing at least aluminum and copper |
| US5911836A (en) * | 1996-02-05 | 1999-06-15 | Mitsubishi Gas Chemical Company, Inc. | Method of producing semiconductor device and rinse for cleaning semiconductor device |
| CN1725458A (en) * | 2004-07-22 | 2006-01-25 | 中芯国际集成电路制造(上海)有限公司 | Method for removing lattice defect in pad area of semiconductor device |
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| CN102569023A (en) | 2012-07-11 |
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Effective date of registration: 20211210 Address after: 315800 No. 79, Qingshan Road, Chaiqiao street, Beilun District, Ningbo City, Zhejiang Province Patentee after: Ningbo Anji Microelectronics Technology Co.,Ltd. Address before: 201203, room 5, building 3000, 613-618 East Avenue, Zhangjiang hi tech park, Shanghai, Pudong New Area Patentee before: ANJI MICROELECTRONICS (SHANGHAI) Co.,Ltd. |