KR20170053191A - Cleaning composite of semiconductor wafer and display panel and manufacturing method thereof - Google Patents
Cleaning composite of semiconductor wafer and display panel and manufacturing method thereof Download PDFInfo
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- KR20170053191A KR20170053191A KR1020150155092A KR20150155092A KR20170053191A KR 20170053191 A KR20170053191 A KR 20170053191A KR 1020150155092 A KR1020150155092 A KR 1020150155092A KR 20150155092 A KR20150155092 A KR 20150155092A KR 20170053191 A KR20170053191 A KR 20170053191A
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/22—Organic compounds
- C11D7/32—Organic compounds containing nitrogen
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/02—Inorganic compounds
- C11D7/04—Water-soluble compounds
- C11D7/10—Salts
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/22—Organic compounds
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02041—Cleaning
- H01L21/02043—Cleaning before device manufacture, i.e. Begin-Of-Line process
- H01L21/02052—Wet cleaning only
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02041—Cleaning
- H01L21/02057—Cleaning during device manufacture
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Abstract
Description
The present invention relates to a composition for cleaning a semiconductor wafer and a display panel which can be cleaned in a single step and has an improved etching rate, and a method for manufacturing the same.
A common metal chemical mechanical polishing (CMP) process forms an oxide film by the oxidizing agent in the slurry and particles in the slurry are removed by applying a higher pressure to the excess area of the wafer or panel surface do. However, as the polishing progresses, the non-oxidized metal particles and the abrasive can be re-adsorbed, which acts as a foreign material. In particular, since the manufacturing process of the display panel repeats the micromachining process of micron unit (탆) on the substrate, if the substrate is contaminated with fine particles and organic matter, it adversely affects the microfabrication process and it becomes impossible to construct a stable production line. Therefore, research on a post CMP cleaning process for removing foreign substances after polishing has been emphasized.
On the other hand, in the display process, cleaning is an important process that accounts for about 30% of the entire process and thus the production yield. In addition, as the panel becomes larger and thinner, higher cleanliness of the surface of the liquid crystal panel is required. In the cleaning process, development of techniques for achieving high productivity and cost saving by shortening the cleaning step and time is actively under way. For example, efforts have been made to improve the detergency by switching from a conventional horizontal cleaning method to a slanting method, and efforts are being made to establish optimal cleaning processing conditions for reducing management costs.
In addition, the development of cleaning technology with an improvement in cleaning efficiency to overcome the decrease in yield due to small contaminating particles of 1 μm unit has resulted in environmental contamination due to the generation of wastewater due to the use of a large amount of ultrapure water, And the increase in the cost of the process. In addition, there is no solution for simultaneously treating the etched metal inorganic material and the organic material used as the abrasive, and a two-step cleaning process has been introduced, resulting in an increase in process time and cost. In addition, in the display manufacturing process, which will be developed in 10 nm class semiconductors, 8 generations (220 × 250 cm 2 ), 10 generations (288 × 313 cm 2 ) and 11 generations (300 × 332 cm 2 ) It is expected that the material used is very fine and the size of critical particles to be cleaned becomes small so that not only the removal rate of particles after cleaning is deteriorated but also the technique of monitoring the removal degree is difficult. It also minimizes impact on wafers or glasses during cleaning, so that there is no physical, electrical, or pattern damage. Therefore, development of damage-free micro cleaning technology will be a major position in semiconductor and display manufacturing process development.
Prior art related to this is a cleaning liquid composition disclosed in Korean Patent Laid-open Publication No. 10-2015-0030196 (published on May 5, 2015.19), a cleaning method of a semiconductor element, and a manufacturing method of a semiconductor element.
Accordingly, it is an object of the present invention to provide a composition for cleaning a semiconductor wafer and a display panel which can be cleaned without damaging a large-area semiconductor wafer and a display panel, and a method for manufacturing the same.
The problems to be solved by the present invention are not limited to the above-mentioned problem (s), and another problem (s) not mentioned can be understood by those skilled in the art from the following description.
In order to solve the above problems, the present invention provides a composition for cleaning a semiconductor wafer and a display panel comprising an organic material removing agent, a complexing agent for preventing metal adsorption, an alkali solution and water.
In addition, the present invention provides a method for producing an organic material removing apparatus, comprising: mixing an organic material removing agent with water; adding an alkali solution so that the pH of the mixed solution of organic material removing agent and water is 8 to 12; And adding a complexing agent for preventing metal adsorption after adding the alkali solution and adding an alkali solution so that the pH is 8 to 12. The present invention also provides a method of manufacturing a composition for cleaning a semiconductor wafer and a display panel.
According to the present invention, the cleaning process can be used for a large-area semiconductor wafer and a display panel, can be cleaned without damage, has a superior organic and inorganic particle removal power compared to conventional commercial cleaning liquids, It is possible to drastically reduce the processing time and cost.
In addition, it is possible to prevent the problem that the organic material removing agent and the complexing agent for preventing metal adsorption are not dissolved by mixing the organic material removing agent, adding an alkali solution, mixing a complexing agent for preventing metal adsorption, and then adding an alkali solution have.
1 is a flowchart showing a method of manufacturing a composition for cleaning a semiconductor wafer and a display panel according to the present invention.
Fig. 2 is a photograph showing the solution state after mixing n-methylpyrrolidone with TFD4-1. Fig.
3 is a graph showing changes in zeta potential of residual particles according to pH of a composition for cleaning a semiconductor wafer and a display panel according to the present invention.
4 is a graph showing etch rates of conventional commercial cleaning liquids with time.
FIG. 5 is a graph showing etching rates of L-glutamic acid, NMP and KOH mixed with time in a composition for cleaning a semiconductor wafer and a display panel according to the present invention.
6 is a graph showing etching rates of K-gluconate, NMP, and KOH mixed with time in a composition for cleaning a semiconductor wafer and a display panel according to the present invention.
7 is a graph showing etching rates of EDTA, NMP and KOH mixed with time in a composition for cleaning a semiconductor wafer and a display panel according to the present invention.
Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS The advantages and features of the present invention and the manner of achieving it will become apparent with reference to the embodiments described in detail below with reference to the accompanying drawings.
The present invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art. To fully disclose the scope of the invention to those skilled in the art, and the invention is only defined by the scope of the claims.
In the following description, well-known functions or constructions are not described in detail since they would obscure the invention in unnecessary detail.
The present invention provides a semiconductor wafer and a composition for cleaning a display panel comprising an organic material removing agent, a complexing agent for preventing metal adsorption, an alkali solution and water.
The composition for cleaning a semiconductor wafer and a display panel according to the present invention can be used for cleaning after etching a silicon wafer, cleaning after a CMP process of a semiconductor substrate, cleaning of a display panel, and the like, .
The composition for cleaning a semiconductor wafer and a display panel according to the present invention can be used for a large-area semiconductor wafer and a display panel, can be cleaned without damage, has superior ability to remove organic and inorganic particles from conventional cleaning liquids, It is possible to reduce the cleaning process that has been going through to a single stage, which can drastically reduce the processing time and cost.
In the composition for cleaning a semiconductor wafer and a display panel according to the present invention, the organic substance removing agent is included to remove organic substances present in the semiconductor wafer and the display panel. The organic material removing agent may be normal methyl pyrrolidone (NMP), and the organic material removing agent is preferably mixed in a volume ratio of 0.02 to 0.06 with respect to water. When the volume ratio is less than 0.02, there is a problem that the organic substances present in the semiconductor and the display panel are not completely removed. When the volume ratio is more than 0.06, the etching rate decreases and the manufacturing cost increases.
Further, the complexing agent for preventing metal adsorption stably forms a complex compound with the metal material in the alkali solution and is used for removing the residual particles. The complexing agent for preventing metal adsorption may be at least one element selected from the group consisting of L-glutamic acid, K-gluconate and ethylenediaminetetraacetic acid, and the complexing agent for preventing metal adsorption may have a concentration of 0.3 to 0.9 M. When the concentration is less than 0.3M, the etching rate is low. When the concentration is more than 0.9M, the manufacturing cost of the semiconductor and display panel cleaning composition increases greatly.
The alkali solution is included to prevent the etched aluminum or copper from being re-adsorbed to the substrate and to control the pH of the mixed solution. The alkali solution may be one selected from the group consisting of potassium hydroxide, sodium hydroxide, carbonate, phosphate, tetramethylammonium hydroxide and tetraethylammonium hydroxide. The alkali solution may be adjusted so that the pH of the composition is 8 to 12 Is preferably added. When the pH is outside the range of 8 to 12, there is a problem that the cleaning effect and the etching rate are lowered.
The composition for cleaning a semiconductor wafer and a display panel according to the present invention may further comprise a corrosion inhibitor, wherein the corrosion inhibitor is selected from the group consisting of benzotriazole, 5-aminotetrazole and 3- Triazole, and 3-amino-1,2,4-triazole.
Further, the present invention relates to a method for preparing an organic-inorganic hybrid material, which comprises mixing an organic matter-removing agent with water, adding an alkaline solution so that the pH of the mixed solution of the organic matter-removing agent and water is 8 to 12; And
And a step of adding a complexing agent for preventing metal adsorption after adding the alkali solution and adding an alkali solution so that the pH is 8 to 12. The present invention also provides a method of manufacturing a composition for cleaning a semiconductor wafer and a display panel.
The method for preparing a composition for cleaning a semiconductor wafer and a display panel according to the present invention is characterized in that when an alkali solution is added after mixing an organic material removing agent and a complexing agent for preventing metal adsorption, the organic material removing agent and the complexing agent for preventing metal adsorption are not dissolved The organic solution removing agent is mixed with the alkali solution, the complexing agent for preventing metal adsorption is mixed, and the alkali solution is added.
1 is a flowchart showing a method of manufacturing a composition for cleaning a semiconductor wafer and a display panel according to the present invention. Hereinafter, the present invention will be described in detail with reference to Fig.
The method for preparing a composition for cleaning a semiconductor wafer and a display panel according to the present invention includes a step (S10) of mixing an organic matter remover with water and adding an alkali solution so that the pH of the mixed solution of the organic matter remover and water is 8 to 12 do.
The kind and content of the organic material removing agent are as described above, and the organic material removing agent may be dissolved by adding an alkali solution so that the pH of the mixed solution of the organic material removing agent and water is 8 to 12.
Next, a method for manufacturing a composition for cleaning a semiconductor wafer and a display panel according to the present invention includes a step (S20) of adding a complexing agent for preventing metal adsorption after addition of the alkali solution and adding an alkali solution so that the pH is 8 to 12 do.
When the complexing agent for preventing metal adsorption is L-glutamic acid, the concentration of L-glutamic acid is preferably 0.5 to 0.9 M. When the complexing agent for preventing metal adsorption is K-gluconate, it is preferably 0.5 to 0.9. When the complexing agent is ethylenediamine tetra In the case of acetic acid, the concentration is preferably 0.3 to 0.7 M. The reason for the limitation as described above is to improve the etching rate and reduce the cost as described in Experimental Example 3 below.
Example 1: Preparation of composition for cleaning semiconductor wafer and display panel 1
N-methyl-2-pyrrolidone (NMP) was used as an organic material removing agent, and L-glutamic acid was mixed with a complexing agent for preventing metal adsorption, Lt; / RTI > Specifically, 40 mL of normal methyl pyrrolidone was added to 1 L of water, calcium hydroxide was added thereto so that the pH of the solution became 8 to 12, L-glutamic acid in the solution was added so as to have a pH of 0.5 to 0.9 M, Of 8 to 12 by adding calcium hydroxide to prepare a cleaning composition.
Example 2: Preparation of composition for cleaning semiconductor wafer and
A cleaning composition was prepared in the same manner as in Example 1 except that K-gluconate was added as a complexing agent for preventing metal adsorption. At this time, the concentration of K-gluconate in the solution was 0.5 to 0.9 M.
Example 3: Preparation of composition for cleaning semiconductor wafer and display panel 3
A cleaning composition was prepared in the same manner as in Example 1, except that ethylenediaminetetraacetic acid (EDTA) was added as a complexing agent for preventing metal adsorption. At this time, the concentration of ethylenediaminetetraacetic acid in the solution was 0.3 to 0.7 M.
Comparative Example 1
A cleaning composition was prepared in the same manner as in Example 1, except that citric acid was added as a complexing agent for preventing metal adsorption.
Comparative Example 2
A cleaning composition was prepared in the same manner as in Example 1, except that tartaric acid was added as a complexing agent for preventing metal adsorption.
Comparative Example 3
A cleaning composition was prepared in the same manner as in Example 1, except that sodium catecholide sulfonic acid was added as a complexing agent for preventing metal adsorption.
Comparative Example 4
A cleaning composition was prepared in the same manner as in Example 1 except that sodium pyrophosphate was added as a complexing agent for preventing metal adsorption.
Experimental Example 1: Analysis of the presence or absence of precipitate formation according to the cleaning composition
The presence or absence of the precipitate formation according to the cleaning composition in the composition for cleaning semiconductor wafer and display panel according to the present invention was analyzed and the results are shown in Table 1.
As shown in Table 1, when L-glutamic acid, K-gluconate, and ethylenediamine tetraacetate (EDTA) were used as a complexing agent for preventing metal adsorption, N-methyl-2-pyrrolidone , NMP), so that precipitates are not formed. However, when citric acid, tartaric acid, sodium catechol di-sulfonate, and sodium pyrophosphate are used, precipitates are formed and are not suitable as a cleaning solution.
Meanwhile, in the conventional cleaning process, cleaning is performed using n-methylpyrrolidone for organic material etching and then cleaning is performed using TFD4-1 for inorganic etching. In order to reduce the two-step cleaning process, n-methylpyrrolidone When two solutions of TFD4-1 are mixed, a precipitate forms. FIG. 2 is a photograph showing the solution state after mixing n-methylpyrrolidone with TFD4-1. As shown in FIG. 2, a white precipitate is formed as described above.
Experimental Example 2: Analysis of Zeta Potential Change of Residual Particles by pH of Cleaning Composition
The zeta potential change of the residual particles according to the pH of the composition for cleaning semiconductor wafer and display panel according to the present invention was analyzed, and the results are shown in FIG.
As shown in FIG. 3, it can be seen that the zeta potential increases as the pH of the cleaning composition increases. Since the zeta potential at pH 11 is the highest, the zeta potential at
Experimental Example 3: Analysis of etching performance of cleaning composition for semiconductor wafer and display panel
In order to examine the etching performance of the composition for cleaning semiconductor wafers and display panel according to the present invention, the etching rates were analyzed and the results are shown in FIGS.
In order to analyze the etching rate, a substrate having a thickness of 0.1 탆 was deposited on a coupon wafer of 1.5 × 1.5
4 is a graph showing the etch rate of the conventional commercial cleaning liquid with time, and Table 2 shows the etch rate obtained from FIG.
As shown in FIG. 4 and Table 2, it can be seen that TFD4-1, which is an inorganic cleaning solution, shows an increase in Al content in solution and an etching rate of 1.05 nm / min over time. TFD4-1 40 ml And 40 ml of NMP showed an etching rate of 0.49 nm / min. However, since the precipitate is formed as described above, it is not suitable. The mixture of 40 ml of KOH and 40 ml of NMP showed 0.42 nm / min and no etching of 40 ml of NMP.
FIG. 5 is a graph showing the etching rates of L-glutamic acid, NMP and KOH in the composition for cleaning semiconductor wafers and display panel according to the present invention with time, and Table 3 shows the etching rates obtained from FIG.
As shown in FIG. 5 and Table 3, it can be seen that as the concentration of L-glutamic acid increases, the etching rate increases. It can be seen that the precipitate is not formed when mixed with NMP, and the etching can be performed, so that it is possible to perform a single step cleaning.
6 is a graph showing the etch rates of K-gluconate, NMP and KOH mixed with time in the composition for cleaning semiconductor wafer and display panel according to the present invention, and Table 4 shows the etch rates obtained from FIG. 6 .
As shown in FIG. 6 and Table 4, it can be seen that as the concentration of K-gluconate increases, the etching rate increases, and precipitates are not formed when mixed with NMP, Able to know.
FIG. 7 is a graph showing the etching rates of EDTA, NMP and KOH mixed with time in the semiconductor wafer and the display panel cleaning composition according to the present invention, and Table 5 shows the etching rates obtained from FIG.
7 and Table 5, it can be seen that as the concentration of EDTA increases, the etching rate increases, and the etching rate at EDTA concentration of 0.5 to 0.7M is higher than that of TFD4-1 and NMP It can be seen that one step cleaning is possible.
As described above, the etching rate increases as the concentration of the complexing agent for preventing metal adsorption increases. However, since the cost of the cleaning composition increases as the concentration increases due to the high price of the complexing agent for preventing metal adsorption, .
Although the present invention has been described with respect to specific examples of the composition for cleaning a semiconductor wafer and a display panel and a method for manufacturing the same, it is obvious that various modifications may be made without departing from the scope of the present invention.
Therefore, the scope of the present invention should not be limited to the above-described embodiments, but should be determined by the scope of the appended claims and equivalents thereof.
It is to be understood that the foregoing embodiments are illustrative and not restrictive in all respects and that the scope of the present invention is indicated by the appended claims rather than the foregoing description, It is intended that all changes and modifications derived from the equivalent concept be included within the scope of the present invention.
Claims (10)
Wherein the organic material removing agent is normal methyl pyrrolidone (NMP).
Wherein the organic material removing agent is mixed in a volume ratio of 0.02 to 0.06 with respect to the water.
Wherein the complexing agent for preventing metal adsorption is at least one selected from the group consisting of L-glutamic acid, K-gluconate, and ethylenediamine tetraacetic acid.
Wherein the complexing agent for preventing metal adsorption has a concentration of 0.3 to 0.9 M in the composition.
Wherein the alkali solution is one selected from the group consisting of potassium hydroxide, sodium hydroxide, carbonate, phosphate, tetramethylammonium hydroxide, tetraethylammonium hydroxide, and the like.
Wherein the alkali solution is added so that the pH of the composition is from 8 to 12. The composition for cleaning a semiconductor wafer and a display panel according to claim 1,
Wherein the cleaning composition further comprises a corrosion inhibitor.
The corrosion inhibitor may be selected from the group consisting of benzotriazole, 5-aminotetrazole and 3-amino-1,2,4-triazole. And the composition for cleaning the semiconductor wafer and the display panel.
And adding a complexing agent for preventing metal adsorption after adding the alkali solution and adding an alkali solution so that the pH is 8 to 12. The method for manufacturing a composition for cleaning a semiconductor wafer and a display panel according to claim 1,
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