CN114326333A - Polyvinyl alcohol cinnamate type KPR photoresist etching residue stripping agent composition - Google Patents
Polyvinyl alcohol cinnamate type KPR photoresist etching residue stripping agent composition Download PDFInfo
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- CN114326333A CN114326333A CN202111669888.4A CN202111669888A CN114326333A CN 114326333 A CN114326333 A CN 114326333A CN 202111669888 A CN202111669888 A CN 202111669888A CN 114326333 A CN114326333 A CN 114326333A
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Abstract
The invention discloses a polyvinyl alcohol cinnamate KPR photoresist etching residue remover composition, which comprises the following components in percentage by weight: 40-70% of organic solvent, 1-20% of organic amine, 0.5-10% of corrosion inhibitor, 0.2-5% of surfactant, 1-5% of fluoride and the balance of ultrapure water, wherein: the surfactant is one or more of ethylene glycol, glycerol, glucose, sorbitol, pentaerythritol, xylitol and AEO-7; the organic amine is one or a mixture of more of monoethanolamine, triethanolamine and isopropanolamine; the corrosion inhibitor is one or a mixture of phenols, carboxylic acids and benzotriazole. The stripping agent has higher cleaning efficiency, obviously shortens the cleaning time compared with similar products, has better cleaning effect and better protection effect on wafer base materials, and can obviously reduce the operation cost of a semiconductor factory.
Description
Technical Field
The invention belongs to the technical field of semiconductor photoresist strippers, and particularly relates to a fluorine-containing quick stripper for removing KPR type photoresist etching residues.
Background
In the production of semiconductor chips, it is necessary to transfer the designed pattern from the mask to the wafer by photolithography and etching, so as to produce the ultra-high integrated chip. The specific process is to deposit a film (including silicon dioxide, silicon nitride, polysilicon, silicon carbide, gallium nitride, titanium nitride, cobalt, tungsten, copper, aluminum, nickel, etc.) on the wafer, apply photoresist, expose, develop, ion implant or etch, ash, clean. In the ion implantation or etching process, the photoresist becomes hard to remove due to ion bombardment, and the etching process leaves a large amount of polymer byproducts on the wafer, so that the photoresist layer can be removed even in the subsequent ashing step, and the remaining byproducts can only be used for thoroughly cleaning the wafer depending on the cleaning process.
In the front-end cleaning process (i.e., before formation of the metal interconnect layer), a mixture of sulfuric acid and hydrogen peroxide is typically used to remove residues after etching or ion implantation. After the metal interconnection layer is formed, neither the aluminum interconnection process nor the copper interconnection process can adopt the method of the front-end cleaning process, and the wafer must be cleaned by adopting a special stripping agent. Obviously, the special stripper used in the back-end process must take into account that the substrate of the wafer itself, especially the aluminum or copper metal, as well as silicon dioxide and silicon nitride, must not be too damaged, in addition to completely cleaning the residues after etching.
At present, the most main photoresist of our company is polyvinyl alcohol cinnamate type KPR series photoresist, which has the advantages of high resolution, strong etching resistance and adhesion, and the like, but after etching-ashing, the conventional back-end stripping liquid is still easy to remain after cleaning, so that the cleaning time is often long and usually reaches more than 20min, and the wafer substrate is also corroded and damaged along with the prolonging of the cleaning time. With the development of advanced processes, the complexity of metal interconnection processes is higher and higher, the number of layers is higher and higher, and the number of cleaning times required by the production of single wafers is higher and higher. Longer cleaning times can result in higher equipment occupancy rates, thereby forcing semiconductor factories to purchase more equipment and occupy more clean rooms to meet the growing cleaning needs. The purchase of semiconductor equipment, the use of strippers, and the operation of clean rooms are all significant components of the operating costs of semiconductor factories. Therefore, reducing the cleaning time and improving the cleaning efficiency are one of the important means for reducing the cost of the semiconductor factory.
Disclosure of Invention
The purpose of the invention is as follows: in view of the above-mentioned problems and disadvantages of the prior art, it is an object of the present invention to provide a polyvinyl alcohol cinnamate type KPR photoresist etching residue remover composition.
The technical scheme is as follows: in order to realize the purpose, the invention adopts the following technical scheme: a polyvinyl alcohol cinnamate type KPR photoresist etching residue remover composition comprises:
and the balance of ultrapure water, the sum of the mass percentages of the components is 100 percent, wherein:
the surfactant is one or more of ethylene glycol, glycerol, glucose, sorbitol, pentaerythritol, xylitol and AEO-7;
the organic solvent is one or a mixture of ethers, ketones and amides;
the organic amine is one or a mixture of more of monoethanolamine, triethanolamine and isopropanolamine;
the corrosion inhibitor is one or a mixture of phenols, carboxylic acids and benzotriazole;
the fluoride is one or a mixture of ammonium bifluoride, tetramethyl ammonium fluoride, tetraethyl ammonium fluoride, tetrabutyl ammonium fluoride, hydrogen fluoride and ammonium fluoride.
Preferably, the surfactant is one or more of AEO-7, glycerol, pentaerythritol, sorbitol, ethylene glycol, glucose and xylitol.
Preferably, the surfactant is a mixture of glycerol and pentaerythritol.
Preferably, the ether organic solvent is one or more of diethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether and dipropylene glycol monobutyl ether.
Preferably, the ketone organic solvent is one or more of acetone, imidazolidinone, pyrrolidone and imidazolidinone.
Preferably, the amide organic solvent is dimethylformamide and/or dimethylacetamide.
Preferably, the corrosion inhibitor is one or a mixture of more of sodium benzoate, methylbenzotriazole, sebacic acid, ethylenediamine tetraacetic acid, sodium nitrite, gallic acid and 1, 2-dihydroxy phenol.
Preferably, the corrosion inhibitor is any combination of benzoic acid and methylbenzotriazole, sodium benzoate and sebacic acid, and sebacic acid/sodium nitrite.
Preferably, the polyvinyl alcohol cinnamate type KPR photoresist etching residue remover composition comprises the following components in percentage by mass:
and the balance of ultrapure water, the sum of the mass percentages of the components is 100 percent, wherein:
the corrosion inhibitor is any combination of sodium benzoate and methylbenzotriazole in a mass ratio of 1:1, sodium benzoate and sebacic acid, sebacic acid and sodium nitrite;
the surfactant adopts glycerol and pentaerythritol in a mass ratio of 1:1, or adopts fatty alcohol polyoxyethylene ether AE 0-7.
The invention also provides a method for removing the photoresist etching residues by applying the stripper composition, which comprises the steps of carrying out contact cleaning on the stripper and a semiconductor chip subjected to etching and ashing by a spraying mode at the temperature of 20-60 ℃, then carrying out oscillation treatment by adopting an ultrasonic wave, megasonic waves, shaking or rotating oscillation mode, rinsing by pure water or ultrapure water at the temperature of 10-30 ℃, and finally carrying out centrifugal drying and/or IPA steam drying.
Has the advantages that: compared with the prior art, the stripping agent can be applied to a semiconductor chip cleaning process adopting a KRP photoresist structure as aluminum interconnection or copper interconnection, can quickly clean photoresist residues after etching and ashing of semiconductor chips, obviously shortens the cleaning time compared with similar products, has good cleaning effect and wafer substrate protection effect, and can obviously reduce the operation cost of a semiconductor factory.
Detailed Description
The present invention is further illustrated by the following examples, which are intended to be purely exemplary and are not intended to limit the scope of the invention, as various equivalent modifications of the invention will occur to those skilled in the art upon reading the present disclosure and fall within the scope of the appended claims.
Examples 1 to 39
The KPR photoresist etching residue stripping agent disclosed by the embodiment 1-39 of the invention is prepared by mixing the components and the proportion shown in the tables 1 and 2. Examples 1-10 test the effect of different surfactants on cleaning performance; examples 11-21 test the effect of different corrosion inhibitor combinations on the cleaning effect and the corrosion of test pieces; the rest is used for discussing the influence of other components and proportions on the cleaning effect of KPR photoresist residues.
Table 1 shows the constituent materials of the release agents of examples 1 to 33
Table 2 shows the mass percentage of each component and the cleaning time in examples 1 to 33.
Comparative examples 1 to 17:
the components and proportions of the photoresists of comparative examples D1-D17 according to the invention are shown in tables 3 and 4. Wherein, the comparative examples 1 to 12 are mainly used for evaluating and discussing the influence of the cleaning effect of the stripping agent without the surfactant; comparative examples 13-17 were used for cleaning effect under non-polyol surfactants.
Table 3 shows the composition of the resist compositions of comparative examples D1-D17
Table 4 shows the contents of the respective components in the photoresists of comparative examples D1 to D15
Stripping agent cleaning test method and evaluation:
1. and (3) cleaning and cleaning effect test of the stripping agent of the semiconductor chip after etching and ashing: after the above embodiments and comparative examples are mixed uniformly according to the proportion and filtered, 5L of the mixture is placed in a spray type cleaning device, a semiconductor chip etched and ashed by adopting KPR photoresist sold in south Jiangsu, a method of spraying is adopted to clean the semiconductor chip; rinsing with ultrapure water after cleaning; and drying in a centrifugal drying mode after rinsing. And finally, detecting the cleaning effect by using an SEM. Each example and comparative example was cleaned for 1 minute and 30 minutes one piece, and the cleaning results are shown in tables 5 and 6.
2. And (3) testing the corrosion effect of different blank wafers:
the method for testing the corrosion conditions of the blank wafer metal aluminum, the blank wafer metal copper, the blank wafer metal titanium and the blank wafer metal tungsten comprises the following steps:
measuring the surface resistance of a 4x4cm blank wafer by using a four-point probe instrument to obtain a film thickness pre-value, immersing the wafer with the pre-value into a stripping agent with the constant temperature of 30-60 ℃, taking out the wafer after 30 minutes, rinsing the wafer by using ultrapure water, drying the wafer by using high-purity nitrogen, measuring the surface resistance of the wafer by using the four-point probe instrument to obtain a thickness post-value of the cleaned film, and calculating to obtain the corrosion rate of the stripping agent on the metal aluminum film.
Tetraethoxysilane (TEOS) blank wafer, silicon nitride (PE Si) blank wafer3N4) The corrosion condition test method comprises the following steps:
the etching condition of Tetraethoxysilane (TEOS) of the blank wafer is specifically operated as follows: measuring the thickness pre-value of a 4x4cm blank TEOS wafer by using FE3000, immersing the TEOS wafer with the pre-value into a stripping agent with the constant temperature of 30-60 ℃, taking out the TEOS wafer after 30 minutes, rinsing the TEOS wafer by using ultrapure water, drying the TEOS wafer by using high-purity nitrogen, measuring the thickness post-value of the TEOS film by using FE3000, and calculating the corrosion rate of the stripping agent on the TEOS film, wherein the corrosion results are shown in tables 5 and 6.
For blank wafer silicon nitride (PE Si)3N4) The specific operation of the corrosion conditions of (1): measuring the thickness pre-value of a 4x4cm blank silicon nitride wafer by using FE3000, immersing the silicon nitride wafer with the pre-value into a stripping agent with the constant temperature of 30-60 ℃, taking out the silicon nitride wafer after 30 minutes, rinsing the silicon nitride wafer by using ultrapure water, drying the silicon nitride wafer by using high-purity nitrogen, measuring the thickness post-value of a silicon nitride film by using FE3000, and obtaining the corrosion rate of the stripping agent to the silicon nitride film by calculation, wherein the corrosion test results are shown in tables 5 and 6.
Table 5 shows the etching effect of different blank wafers after being cleaned by the stripping solution of the present invention
Table 6 shows the corrosion effect of different blank wafers after being cleaned by the stripping solutions of different comparative examples
The meanings of the symbols in tables 5 and 6
From the comparison of the cleaning results of the above examples B1-B33 and comparative examples D1-D15, it can be seen that:
from the results of comparative examples D1-D15, it can be seen that the stripping solution without surfactant still has more photoresist residue after 10min cleaning, and the cleaning effect of the added surfactants such as 5-sulfosalicylic acid, isooctyl alcohol ether phosphate, sodium dodecylbenzene sulfonate, distyrylphenol polyoxyethylene ether, and vinyl bis stearamide is improved, but the effect is different from that of the embodiments 1-33 of the present invention.
The strippers of the embodiments B1-B33 of the invention can be completely stripped without residue after being cleaned for 10min, and the strippers of the embodiments B10-B21 adopting glycerol/pentaerythritol combination or AEO-7 two surfactants can be completely removed without residue after being cleaned for 1min, thereby greatly improving the cleaning efficiency and shortening the cleaning time, so that the strippers can be seen as follows: the stripping agent of the embodiment B1-B33 of the invention obviously improves the cleaning effect of the etching residual glue. In addition, the cleaning effect of the combination of other organic solvents, the surfactant and the corrosion inhibitor is discussed in the embodiments B23-B33 of the invention, and the results show that the complete removal can be achieved within 10min of cleaning time. From the test results, it can be seen that the corrosion inhibitor using the combination of at least two of sodium benzoate, tolyltriazole, sebacic acid, and sodium nitrite has the optimum corrosion inhibition effect and can achieve the substantially non-corrosive effect.
The stripping agent can obviously improve the cleaning efficiency of the semiconductor chip, and is beneficial to reducing the occupancy rate of cleaning equipment in a semiconductor factory, thereby achieving the effects of reducing the purchase of the cleaning equipment and reducing the production and operation costs.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are only exemplary embodiments of the present invention, and are not intended to limit the present invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A polyvinyl alcohol cinnamate type KPR photoresist etching residue remover composition is characterized by comprising:
40-70% of organic solvent
1 to 20 percent of organic amine
0.5 to 10 percent of corrosion inhibitor
0.2 to 5 percent of surfactant
1 to 5 percent of fluoride
And the balance of ultrapure water, the sum of the mass percentages of the components is 100 percent, wherein:
the surfactant is one or more of ethylene glycol, glycerol, glucose, sorbitol, pentaerythritol, xylitol and AEO-7;
the organic solvent is one or a mixture of ethers, ketones and amides;
the organic amine is one or a mixture of more of monoethanolamine, triethanolamine and isopropanolamine;
the corrosion inhibitor is one or a mixture of phenols, carboxylic acids and benzotriazole;
the fluoride is one or a mixture of ammonium bifluoride, tetramethyl ammonium fluoride, tetraethyl ammonium fluoride, tetrabutyl ammonium fluoride, hydrogen fluoride and ammonium fluoride.
2. The polyvinyl alcohol cinnamate type KPR photoresist etch residue stripper composition of claim 1, wherein: the surfactant is one or more of AEO-7, glycerol, pentaerythritol, sorbitol, ethylene glycol, glucose and xylitol.
3. The polyvinyl alcohol cinnamate type KPR photoresist etch residue stripper composition of claim 2, wherein: the surfactant is a mixture of glycerol and pentaerythritol.
4. The polyvinyl alcohol cinnamate type KPR photoresist etch residue stripper composition of claim 1, wherein: the ether organic solvent is one or more of diethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether and dipropylene glycol monobutyl ether.
5. The polyvinyl alcohol cinnamate type KPR photoresist etch residue stripper composition of claim 1, wherein: the ketone organic solvent is one or more of acetone, imidazolidinone, pyrrolidone and imidazolidinone.
6. The polyvinyl alcohol cinnamate type KPR photoresist etch residue stripper composition of claim 1, wherein: the amide organic solvent is dimethylformamide and/or dimethylacetamide.
7. The polyvinyl alcohol cinnamate type KPR photoresist etch residue stripper composition of claim 1, wherein: the corrosion inhibitor is one or a mixture of more of sodium benzoate, methylbenzotriazole, sebacic acid, ethylenediamine tetraacetic acid, sodium nitrite, gallic acid and 1, 2-dihydroxy phenol.
8. The polyvinyl alcohol cinnamate type KPR photoresist etch residue stripper composition of claim 7, wherein: the corrosion inhibitor is any combination of benzoic acid and methylbenzotriazole, sodium benzoate and sebacic acid, and sebacic acid/sodium nitrite.
9. The polyvinyl alcohol cinnamate type KPR photoresist etching residue remover composition according to claim 1, which is characterized by comprising the following components by mass percent:
diethylene glycol monomethyl ether 40-60%
5 to 10 percent of triethanolamine
2 to 5 percent of ammonium bifluoride
2 to 5 percent of corrosion inhibitor
2 to 5 percent of surfactant
And the balance of ultrapure water, the sum of the mass percentages of the components is 100 percent, wherein:
the corrosion inhibitor is any combination of sodium benzoate and methylbenzotriazole in a mass ratio of 1:1, sodium benzoate and sebacic acid, sebacic acid and sodium nitrite;
the surfactant adopts glycerol and pentaerythritol in a mass ratio of 1:1, or adopts fatty alcohol polyoxyethylene ether AE 0-7.
10. A method for removing a resist etching residue using the stripper composition according to any one of claims 1 to 9, wherein: and (2) carrying out contact cleaning on the stripping agent and the etched and ashed semiconductor chip by a spraying mode at the temperature of 20-60 ℃, then carrying out oscillation treatment by adopting an ultrasonic wave, megasonic waves, shaking or rotating oscillation mode, rinsing by pure water or ultrapure water at the temperature of 10-30 ℃, and finally carrying out centrifugal drying and/or IPA steam drying to finish the process.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115506030A (en) * | 2022-09-23 | 2022-12-23 | 浙江奥首材料科技有限公司 | Monocrystalline silicon wet etching texturing additive, monocrystalline silicon wet etching texturing solution containing monocrystalline silicon wet etching texturing additive, and preparation method and application of monocrystalline silicon wet etching texturing solution |
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2021
- 2021-12-31 CN CN202111669888.4A patent/CN114326333A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115506030A (en) * | 2022-09-23 | 2022-12-23 | 浙江奥首材料科技有限公司 | Monocrystalline silicon wet etching texturing additive, monocrystalline silicon wet etching texturing solution containing monocrystalline silicon wet etching texturing additive, and preparation method and application of monocrystalline silicon wet etching texturing solution |
| CN115506030B (en) * | 2022-09-23 | 2024-02-27 | 浙江奥首材料科技有限公司 | Monocrystalline silicon wet etching texturing additive, monocrystalline silicon wet etching texturing liquid containing monocrystalline silicon wet etching texturing additive, preparation method and application of monocrystalline silicon wet etching texturing additive |
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