CN103773626B - A kind of cleaning fluid of the removal photoresistance etch residues of low etching - Google Patents
A kind of cleaning fluid of the removal photoresistance etch residues of low etching Download PDFInfo
- Publication number
- CN103773626B CN103773626B CN201210410184.XA CN201210410184A CN103773626B CN 103773626 B CN103773626 B CN 103773626B CN 201210410184 A CN201210410184 A CN 201210410184A CN 103773626 B CN103773626 B CN 103773626B
- Authority
- CN
- China
- Prior art keywords
- cleaning fluid
- ether
- mass percentage
- percentage content
- pyrogallol
- 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
- Cleaning Or Drying Semiconductors (AREA)
- Detergent Compositions (AREA)
Abstract
The invention discloses a kind of cleaning fluid and its composition for removing photoresistance etch residues.The cleaning fluid of the removal photoresistance etch residues of this low etching property contains（a）Hydramine,（b）Alcohol ether, (c) water, (d) pyrogallol and/or its derivative, e）Gallic acid and/or its ester.The cleaning fluid of the removal photoresistance etch residues of this low etching property can remove metal wire simultaneously（metal）, photoresistance residue on through hole (via) and metal gasket (Pad) wafer, do not attacked substantially simultaneously for base material such as metallic aluminium, nonmetallic silica etc..Had a good application prospect in fields such as cleaning semiconductor chips.
Description
Technical field
The present invention relates to a kind of cleaning fluid for removing photoresistance etch residues.
Background technology
In semiconductor components and devices manufacturing process, coating, exposure and the imaging of photoresist layer manufacture to the pattern of component
Say it is necessary processing step.In the last of patterning（Coating i.e. in photoresist layer, after being imaged, be ion implanted and etching）Enter
Before the next processing step of row, the residue of photoresistance layer material need to be removed thoroughly.Can hardening light in doping step intermediate ion bombardment
Resistance layer polymer, hence in so that photoresist layer becomes to not readily dissolve so as to be more difficult to remove.So far in the semiconductor manufacturing industry one
As use two-step method（Dry ashing and wet etching）Remove this layer of photoresistance tunic.The first step removes photoresist layer using dry ashing
（PR）Major part；Second step is removed using composite corrosion inhibitor wet etching/cleaning and washes remaining photoresist layer, its
Step is generally cleaning fluid cleaning/rinsing/drying.The polymer light resistance layer of residual and inorganic can only be removed in this process
Thing, and infringement metal level such as aluminium lamination can not be attacked.
In current wet clean process, cleaning fluid with the most use is the cleaning fluid containing azanol class and fluorinated,
The Exemplary patents of azanol based cleaning liquid have US6319885, US5672577, US6030932, US6825156 and US5419779 etc..
By updating, the corrosion rate of metallic aluminium has been greatly reduced in itself for its solution, but the based cleaning liquid is due to using hydroxyl
Amine, and the problems such as single source, explosive be present in azanol.And although existing fluorides cleaning fluid has larger improvement,
Such as US5,972,862, US 6,828,289 etc., but still the corruption that can not control metal and non-metallic substrate simultaneously well be present
Erosion, easily causes the change of channel characteristics size after cleaning；On the other hand due to wet clean equipment in some Semiconductor enterprises
Be made up of quartz, and fluorine-containing cleaning fluid has corrosion to quartz and corrodes with the rise of temperature aggravation, thus presence with it is existing
The problem of quartzy equipment is incompatible and influence it and widely use.
Although the cleaning fluid of azanol class and fluorinated is relatively applied successfully to semi-conductor industry, due to
Its respective limitation and shortcoming, industry still have developed the cleaning fluid of the 3rd class, this based cleaning liquid neither containing azanol nor
Contain fluoride.As US5988186 is disclosed containing solvent, hydramine, water and nutgall acids and its cleaning fluid of esters, both solved
Determined azanol source is single and safety and environmental protection in terms of the problem of, it is unstable to solve the nonmetallic corrosion rate of fluorine-containing based cleaning liquid again
The problem of determining.But this based cleaning liquid often exists very in use due to both not containing azanol or not containing fluoride
Big limitation.Although therefore disclosing some cleaning liquid compositions, but need and more need to prepare recently to adapt to
The wider array of based cleaning liquid in face.
The content of the invention
The invention aims to provide a kind of inexpensive semiconductor die that can remove the photoresistance residue on wafer
Circle cleaning fluid, it does not contain azanol and fluoride；It is smaller to metal and nonmetallic corrosion rate；And with quartzy hardware compatibility.
The cleaning fluid of the present invention contains：
I. hydramine 40-70%, preferably 50-65%；
Ii. alcohol ether 10-40%, preferably 15-30%；
Iii. water 10-30%, preferably 15-25%；
Iv. pyrogallol and its derivative 0.1-10%, preferably 0.5-5%；
V. gallic acid and its ester, preferably 0.1-5%, 0.5-3%；
Above-mentioned content is mass percentage content, and does not contain azanol and fluoride.
In the present invention, described hydramine is preferably MEA, N- methylethanolamines, diethanol amine, triethanolamine, different
Propanolamine, ethyldiethanolamine, N, N- diethyl ethylene diamines, N- (2- amino-ethyls) monoethanolamines and diglycolamine.
In the present invention, described alcohol ether is preferably diethylene glycol monoalky lether and dipropylene glycol monoalkylether.Wherein, institute
The diethylene glycol monoalky lether stated is preferably diethylene glycol monomethyl ether, diethylene glycol monoethyl ether and diethylene glycol monobutyl ether；Institute
The dipropylene glycol monoalkylether stated is preferably dipropylene glycol monomethyl ether, DPE and Dipropylene glycol mono-n-butyl Ether.From
For the environmental angle of alcohol ether, the preferred dipropylene glycol monoalkylether of described alcohol ether；From all alcohol ethers to photoresistance etch residues
For removal efficiency, described alcohol ether more preferably dipropylene glycol monomethyl ether.
In the present invention, described pyrogallol and/or its derivative are preferably selected from pyrogallol, 5- methyl neighbours benzene three
One or more in phenol, 5- methoxyl groups pyrogallol, 5- tert-butyl os benzenetriol and 5- methylol pyrogallols.
In the present invention, described gallic acid and/or its ester are preferably selected from gallic acid, no gallicin, food
Sub- acetoacetic ester, butyl gallate, octyl gallate, dodecyl gallate and one kind in 1- gallic acid glyceride or
It is a variety of.
Cleaning fluid in the present invention, photoresistance residue that can be at 50 DEG C to 80 DEG C on cleaning wafer.Specific method is such as
Under：Wafer containing photoresistance residue is immersed in the cleaning fluid in the present invention, soaks the suitable time at 50 DEG C to 80 DEG C
Afterwards, dried up after taking out rinsing with high pure nitrogen.
The technical effects of the invention are that：
1）The cleaning fluid of the present invention, can be by pyrogallol and its derivative and gallic acid and its binary built of ester
Effectively remove metal wire（metal）, photoresistance residue on through hole (via) and metal gasket (Pad) wafer simultaneously, realize pair
Metallic aluminium and the suppression of nonmetallic corrosion；
2) cleaning fluid of the invention solves that azanol source in traditional azanol based cleaning liquid is single, expensive, explosive
The problems such as；
3）The cleaning fluid of the present invention is relatively low due to its nonmetallic corrosion rate；Solves traditional nonmetallic corruption of fluorine class cleaning fluid
The problem of speed is unstable is lost, and it is compatible with the quartzy rinse bath that current semiconductor manufacturer generally uses.
Embodiment
Agents useful for same and raw material of the present invention are commercially available.By mentioned component, simply uniformly mixing is the cleaning fluid of the present invention
It can be made.
1 each embodiment of table（Examples）In cleaning fluid component and content
The component and content of cleaning fluid in 2 each comparative example of table
Effect example
In order to further investigate the cleaning situation of the based cleaning liquid, present invention employs following technological means：It will contain
The metal wire of photoresistance residue（metal）Wafer, through hole (via) wafer and metal gasket (Pad) wafer are immersed in cleaning fluid respectively,
Vibrated 10 ~ 30 minutes with about 60 revs/min of vibration frequency using constant temperature oscillator at 50 DEG C to 80 DEG C, then after rinsing is washed
Dried up with high pure nitrogen.The cleaning performance and cleaning fluid of photoresistance residue are as shown in table 2 to the corrosion condition of chip.
The wafer cleaning situation of the section Example of table 3 and comparative example
From table 3 it can be seen that the cleaning fluid of the present invention is to the metal wire containing photoresistance residue（metal）Wafer, through hole
(via) wafer and metal gasket (Pad) wafer have good cleaning performance, and use temperature range is wide, while without corrosion metal
Aluminium and nonmetallic silica.From comparative example 1 and embodiment 11 as can be seen that using conventional dimethylsulfoxide solvent, do not have
The photoresistance residue of wafer can be removed completely, and uses alcohol ether to be advantageous to the removal of photoresistance residue as solvent.From contrast
Example 2, comparative example 3 and embodiment 11 as can be seen that other components are identical, cleaning operation condition is also in the case of identical,
Such as it is added without pyrogallol and its derivative, the photoresistance residue on wafer fails to remove completely；Such as be added without gallic acid and
Its ester, then it can produce the corrosion of metallic aluminium.And add this two classes material simultaneously, then the photoresistance residual on wafer can be removed simultaneously
Thing, the problem of metallic aluminium will not be produced again.From comparative example 4 and embodiment 11 as can be seen that traditional catechol is except inadequate
Outside environmental protection, it adds the corrosion that can cause metallic aluminium.
It should be appreciated that wt% of the present invention refers to weight/mass percentage composition.
The specific embodiment of the present invention is described in detail above, but it is intended only as example, it is of the invention and unlimited
It is formed on particular embodiments described above.To those skilled in the art, it is any to the equivalent modifications that carry out of the present invention and
Substitute also all among scope of the invention.Therefore, the impartial conversion made without departing from the spirit and scope of the invention and
Modification, all should be contained within the scope of the invention.
Claims (9)
1. the cleaning fluid of the removal photoresistance etch residues of a kind of low etching, it is characterised in that the cleaning fluid is by hydramine, alcohol
Ether, pyrogallol and/or its derivative, gallic acid and/or its ester and water composition；
Wherein,
The mass percentage content of the hydramine is 40-70wt%, and the mass percentage content of the alcohol ether is 10-40wt%,
The mass percentage content of the pyrogallol and/or its derivative is 0.1-10wt%, the gallic acid and/or its ester
Mass percentage content is 0.1-5wt%, and the mass percentage content of the water is 10-30wt%.
2. cleaning fluid as claimed in claim 1, it is characterised in that：The mass percentage content of the hydramine is 50-65wt%,
The mass percentage content of the alcohol ether is 15-30wt%, the mass percentage content of the pyrogallol and/or its derivative
For 0.5-5wt%, the mass percentage content of the gallic acid and/or its ester is 0.5-3wt%, the quality percentage of the water
It is 15-25wt% than content.
3. cleaning fluid as claimed in claim 1, it is characterised in that：Described hydramine be selected from MEA, N- methylethanolamines,
Diethanol amine, triethanolamine, isopropanolamine, ethyldiethanolamine, N, N- diethyl ethylene diamines, N- (2- amino-ethyls) monoethanolamine
With the one or more in diglycolamine.
4. cleaning fluid as claimed in claim 1, it is characterised in that：Described alcohol ether is selected from diethylene glycol monoalky lether and dipropyl
Glycol monoalkyl ether.
5. cleaning fluid as claimed in claim 4, it is characterised in that：Described diethylene glycol monoalky lether is diethylene glycol list first
Ether, diethylene glycol monoethyl ether and/or diethylene glycol monobutyl ether；Described dipropylene glycol monoalkylether be dipropylene glycol monomethyl ether,
DPE and/or Dipropylene glycol mono-n-butyl Ether.
6. cleaning fluid as claimed in claim 4, it is characterised in that：Described alcohol ether is dipropylene glycol monoalkylether.
7. cleaning fluid as claimed in claim 6, it is characterised in that：Described alcohol ether is dipropylene glycol monomethyl ether.
8. cleaning fluid as claimed in claim 1, it is characterised in that：Described pyrogallol and/or its derivative are selected from adjacent benzene
One in triphenol, 5- methyl pyrogallol, 5- methoxyl groups pyrogallol, 5- tert-butyl os benzenetriol and 5- methylol pyrogallols
Kind is a variety of.
9. cleaning fluid as claimed in claim 1, it is characterised in that：Described gallic acid and/or its ester be selected from gallic acid,
Gallicin, progallin A, butyl gallate, octyl gallate, dodecyl gallate and 1- nutgalls
One or more in acid glyceride.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210410184.XA CN103773626B (en) | 2012-10-24 | 2012-10-24 | A kind of cleaning fluid of the removal photoresistance etch residues of low etching |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210410184.XA CN103773626B (en) | 2012-10-24 | 2012-10-24 | A kind of cleaning fluid of the removal photoresistance etch residues of low etching |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103773626A CN103773626A (en) | 2014-05-07 |
| CN103773626B true CN103773626B (en) | 2018-01-12 |
Family
ID=50566392
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210410184.XA Active CN103773626B (en) | 2012-10-24 | 2012-10-24 | A kind of cleaning fluid of the removal photoresistance etch residues of low etching |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103773626B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105527803B (en) * | 2014-09-29 | 2020-08-18 | 安集微电子（上海）有限公司 | Photoresist cleaning solution |
| CN115895800A (en) * | 2022-12-14 | 2023-04-04 | 芯越微电子材料(嘉兴)有限公司 | Semi-aqueous wafer substrate cleaning solution composition and application method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101750913A (en) * | 2008-12-05 | 2010-06-23 | 安集微电子（上海）有限公司 | Cleaning solution for removing residues on photoresist layer |
| CN101750916B (en) * | 2008-12-17 | 2013-08-14 | 三星显示有限公司 | Composition for photoresist stripper and method of fabricating thin film transistor array substrate |
| CN101685273B (en) * | 2008-09-26 | 2014-06-04 | 安集微电子（上海）有限公司 | Cleanout fluid for removing photoresist layer residue |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20100062538A (en) * | 2008-12-02 | 2010-06-10 | 삼성전자주식회사 | Composition for photoresist stripper and method of fabricating thin film transistor array substrate |
-
2012
- 2012-10-24 CN CN201210410184.XA patent/CN103773626B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101685273B (en) * | 2008-09-26 | 2014-06-04 | 安集微电子（上海）有限公司 | Cleanout fluid for removing photoresist layer residue |
| CN101750913A (en) * | 2008-12-05 | 2010-06-23 | 安集微电子（上海）有限公司 | Cleaning solution for removing residues on photoresist layer |
| CN101750916B (en) * | 2008-12-17 | 2013-08-14 | 三星显示有限公司 | Composition for photoresist stripper and method of fabricating thin film transistor array substrate |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103773626A (en) | 2014-05-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5860020B2 (en) | Stripping and cleaning composition for removing thick film resist | |
| JP4741315B2 (en) | Polymer removal composition | |
| CN102047184A (en) | Cleaning solution of plasma etching residues | |
| CN105785725A (en) | Photoresist residue cleaning liquid | |
| JP6412143B2 (en) | Stripper composition for removing photoresist and method for stripping photoresist using the same | |
| CN104946429A (en) | Low-etching detergent for removing photoresist etching residues | |
| CN101955852A (en) | Cleaning solution for plasma etching residues | |
| CN101827927B (en) | A plasma etching residues cleaning solution | |
| CN101561641A (en) | Plasma etching residual washing liquid | |
| CN105022237B (en) | Metal low-etching photoresist stripping liquid | |
| CN101666984A (en) | Plasma etching residue cleaning solution | |
| CN101685273B (en) | Cleanout fluid for removing photoresist layer residue | |
| CN103773626B (en) | A kind of cleaning fluid of the removal photoresistance etch residues of low etching | |
| KR101459725B1 (en) | Stripper composition for removing post-etch residues and photoresist etch polymer | |
| CN101295143B (en) | Photoresist leftover cleaning agent | |
| CN108121176A (en) | A kind of low etching photoresist residual washing liquid | |
| CN101424887A (en) | Semiconductor wafer metal substrate web corrosion prevention liquid and its use method | |
| CN106933067A (en) | A kind of photoresistance residual washing liquid composition rich in water | |
| TW201723166A (en) | A cleaning liquid for removing photoresist residue, with little corrosion on base material | |
| CN112470079A (en) | Cleaning method | |
| CN102051283A (en) | Hydroxylamine-containing cleaning solution and use thereof | |
| CN105527803A (en) | Photoresist cleaning fluid | |
| TW201835322A (en) | A cleaning solution comprising fluorine | |
| CN101750913A (en) | Cleaning solution for removing residues on photoresist layer | |
| JP2007183577A (en) | Aqueous alkali photoresist cleaning composition and usage of the composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB02 | Change of applicant information |
Address after: 201201 Pudong New Area East Road, No. 5001 Jinqiao Export Processing Zone (South) T6-9 floor, the bottom of the Applicant after: Anji microelectronic technology (Shanghai) Limited by Share Ltd Address before: 201201 Pudong New Area East Road, No. 5001 Jinqiao Export Processing Zone (South) T6-9 floor, the bottom of the Applicant before: Anji Microelectronics (Shanghai) Co., Ltd. |
|
| CB02 | Change of applicant information | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20211206 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: 201201 T6-9, Jinqiao Export Processing Zone (South District), No. 5001 East China Road, Shanghai, Pudong New Area Patentee before: ANJI MICROELECTRONICS TECHNOLOGY (SHANGHAI) Co.,Ltd. |
|
| TR01 | Transfer of patent right |