KR20030077272A - Method for rinsing of semiconductor device - Google Patents

Abstract

PURPOSE: A method for rinsing a semiconductor device is provided to adapt a rinsing method, of which orientation film printing characteristics and the characteristics for removing organic pollutant layer are best, through the measurement of contact angles of an ITO deposition film or an Ag reflection film, thereby preventing the discoloration for the Ag and improving the PI printing characteristics. CONSTITUTION: A method for rinsing a semiconductor device includes the steps of organic rinsing a substrate deposited with an ITO film, and rinsing the substrate with UV at 200-400nm. In the case of an Ag reflection film is deposited, the organic rinsing is accompanied by the rinsing with deionized water. After the ITO film deposition, TMAH having the concentration of 0.7-5% is used for the rinsing. The organic rinsing is carried out by an organic rinsing solution or a photoresist separation solution containing MEA 20-60wt%, N,N-DMAc 15-50wt%, carbitol 15-50wt%, and gallic acid 0.1-10wt%.

Description

METHODS FOR RINSING OF SEMICONDUCTOR DEVICE

The present invention relates to a method for cleaning a semiconductor device, and more particularly, to a method for cleaning a semiconductor device for removing discoloration of a reflective film of a liquid crystal display device used for removing an organic contamination layer and improving printability of an alignment film (PI). .

A liquid crystal display device is a display device that uses an optical property of a liquid crystal by changing an arrangement of liquid crystal molecules by applying an electric field. In this case, an electrode is required to apply an electric field, and this electrode is required to have conductivity and transparency, and suitable ITO (indium tin oxide) is mainly used. The manufacturing method of the liquid crystal display device is performed by forming a wiring made of a metal, forming a protective film covering the wiring, and laminating and patterning an ITO film to form a transparent electrode.

On the other hand, small and medium-sized liquid crystal display devices employ reflective structures (reflective and transflective) because of their weight and weight. The reflection type transfers images and information with contrast ratio and color reproducibility by using an external light source as a whole, and the transflective type serves as a device applying the advantages of the transmissive type to the advantages of the reflective type. In addition, since an external light source proceeds to the reflective mode without a back light, Al or Ag is used as the reflective film to increase the reflectance. In the case of the small and medium-sized structure using Ag as the reflective film, the reflectance improvement is improved rather than Al, but it is weak in pattern formation, discoloration, and process stability.

In order to solve the problems of the prior art as described above, the present invention provides a cleaning method of a new semiconductor device that can prevent the discoloration of the small and medium-sized reflective film by evaluating the organic contamination layer removal ability and the printability of the alignment film (PI) in the LCD manufacturing process. It aims to provide.

Another object of the present invention is to provide a liquid crystal display device manufactured using the cleaning method.

1 is a photograph of a contact angle measured by DI after ITO deposition, organic cleaning, and UV cleaning in a manufacturing process of a liquid crystal display device.

2 is a photograph of a contact angle measured by DI after ITO deposition, DI cleaning, and UV cleaning in a manufacturing process of a liquid crystal display device.

3 is a photograph of measurement of contact angle by DI after ITO deposition and TMAH cleaning in a manufacturing process of a liquid crystal display device.

FIG. 4 is a photograph of measurement of contact angle by PI after ITO deposition, organic cleaning, and UV cleaning in a manufacturing process of a liquid crystal display.

FIG. 5 is a photograph of measurement of contact angle by PI after ITO deposition and TMAH cleaning in a manufacturing process of a liquid crystal display device. FIG.

FIG. 6 is a photograph of measurement of contact angle by DI by DI cleaning after organic cleaning on Ag film in a manufacturing process of a liquid crystal display. FIG.

7 is a graph illustrating color coordinate changes according to cleaning conditions in a manufacturing process of a liquid crystal display.

In order to achieve the above object, the present invention provides a method for cleaning a semiconductor device, comprising the step of cleaning with tetramethylammonium hydroxide (TMAH) after the deposition of indium tin oxde (ITO) film in the manufacturing process of the liquid crystal display device A cleaning method for a semiconductor device is provided.

In addition, the present invention provides a method for cleaning a semiconductor device, the method of cleaning a semiconductor device comprising the step of cleaning with organic UV after the indium tin oxde (ITO) film deposition in the manufacturing process of the liquid crystal display device.

In addition, the present invention provides a method for cleaning a semiconductor device, the method comprising cleaning the organic semiconductor and cleaning with deionized water (DI) after the Ag reflective film deposition in the manufacturing process of the liquid crystal display device.

In addition, the present invention provides a liquid crystal display device including the cleaning method.

Hereinafter, the present invention will be described in more detail.

The present invention provides a method for cleaning a semiconductor device for a liquid crystal display device that can minimize discoloration of Ag film, stabilize PI printing process, and maximize organic material removal ability by using a contact angle measuring device while changing the cleaning method during the manufacturing process of a liquid crystal display device. It is about. In addition, the present invention relates to a cleaning method of a semiconductor device for a liquid crystal display device in which the cleaning applied after the pixel ITO process is evaluated by applying a contact angle measuring device from the viewpoint of organic contamination and PI printability in the current transmission type structure. .

The liquid crystal display may be manufactured by forming a photoresist pattern on a conductive metal film or an insulating film formed on an insulating substrate, and then cleaning and etching the same to form a fine circuit.

In the present invention, after the formation of the pattern in the manufacturing process of the liquid crystal display device, after applying various cleaning methods, the contact angle is measured by using a contact angle measuring device (contact angle meter) to evaluate organic contaminant removal ability and alignment film printability, and to select and use the most excellent method. do. Accordingly, in the present invention, a cleaning method applied after deposition of pixel indium tin oxide (ITO) and a method of cleaning after deposition of Ag reflective film may be different in a transmissive structure.

In the present invention, the cleaning method after ITO deposition is preferably performed with tetramethylammonium hydroxide (TMAH).

The concentration of tetramethylammonium hydroxide (TMAH) used in the present invention is preferably 0.7 to 5%, more preferably 2.38%. At this time, when the TMAH concentration is out of the range, the discoloration of the reflective film is severe and corrosion occurs.

In addition, it is preferable that the contact angle measurement value of a general semiconductor device including a liquid crystal display device is lower than 30 °. The reason is that a high contact angle measurement value does not remove organic contaminants of the reflective film, which causes problems in subsequent processes and the alignment film printability. Because it is not good.

Therefore, when the cleaning method according to the present invention is used, the contact angle measurement value is lower than the above level, thereby preventing discoloration of the reflective film. Preferably, the contact angle measurement is less than or equal to 15 ° when washed with tetramethylammonium hydroxide. Therefore, according to the present invention, the polyimide solution used for printing the alignment film has a contact angle measurement value of 6 ° or less, thereby improving printability.

In addition, the cleaning method after ITO deposition of the present invention includes a method of UV cleaning after organic cleaning.

In the present invention, the wavelength of the UV light used in the UV cleaning is preferably in the range of 200 to 420 nm, and if the wavelength range of the UV light is out of the above range, the cleaning effect of organic matter removal cannot be seen.

The present invention can improve both the organic layer removal ability and the alignment film printability through the cleaning method after ITO deposition. In this case, the cleaning method capable of improving the organic pollutant removal ability may further include a method of UV cleaning after washing with DI water. In addition, an organic cleaning method may be further included to improve the alignment film (PI) printability.

In addition, in the present invention, the cleaning method after deposition of Ag is preferably carried out after deionized water cleaning after organic cleaning. At this time, only the organic cleaning method may be used.

In the present invention, the cleaning solution used after ITO deposition or Ag deposition is 20 to 60% by weight of monoethanolamine, 15 to 50% by weight of N, N-dimethylacetamide, and 15 to 50% by weight of carbitol. It is preferable to use an organic cleaning solution or a photoresist stripping solution containing 0.1 to 10% by weight of gallic acid.

The monoethanolamine (MEA) serves to exfoliate the photoresist in the gate process without generating fine particles of impurities. The monoethanolamine may be used in an amount of 20 to 60 wt% based on the total stripper composition, and more preferably 35 to 45 wt%. When the amount of the monoethanolamine used is less than 20% by weight, the peeling performance is lowered, so that the photoresist fine particles remain, and when the amount of the monoethanolamine is greater than 60% by weight, the absorbency to the photoresist is reduced.

The N, N-dimethylacetamide (DMAc) is a component that acts as a strong solvent, it is preferable to use 15 to 50% by weight of the total stripper composition, it is more preferable to use 25 to 35% by weight. If the amount of the N, N-dimethylacetamide used is less than 15% by weight, the solubility of the photoresist is inhibited. If the amount of the N, N-dimethylacetamide is used, the peeling performance of the photoresist is lowered.

The stripper composition for a photoresist of the present invention includes carbitol, which is a diethylene glycol monoethyl ether system with DMAc as an organic solvent. This serves to further enhance the strip performance of the composition containing the monoethanolamine and N, N-dimethylacetamide as well as the solvent for dissolving the photoresist. Carbitol used in the present invention is preferably used in 15 to 50% by weight, more preferably 25 to 35% by weight. If the amount of the carbitol is less than 15% by weight, the stripper composition is not easily absorbed by the photoresist layer. If the amount of the carbitol is more than 50% by weight, the peeling performance of the photoresist may be deteriorated.

In addition, the photoresist stripper composition of the present invention contains gallic acid. The gallic acid serves to prevent the corrosion of silver by suppressing the amount of silver eluted when applied to a gate process using silver (Ag) as a reflective film. The amount of the gallic acid is preferably used in 0.1 to 10% by weight of the total stripper composition, more preferably 1 to 2% by weight. If the amount of the gallic acid used is less than 0.1% by weight, there is a problem that silver is corroded.

According to a preferred embodiment of the present invention, the organic cleaning liquid or stripping liquid is 35 to 45% by weight of monoethanolamine, 25 to 35% by weight of N, N-dimethylacetamide, 25 to 35% by weight of carbitol, and 1 to 2% by weight of gallic acid.

According to the present invention, when the deionized water is washed after the organic cleaning with the organic cleaning liquid or the photoresist (PR) stripping solution during Ag deposition, the contact angle measurement value is lower than 30 °, thereby preventing discoloration of the reflective film. Moreover, according to this invention, the contact angle of the polyimide solution used at the time of printing an orientation film becomes 5 degrees or less, and printability can be improved. In addition, it can be seen that the color coordinate measured using the spectroscopic reflectometer (MCPD) after cleaning of the Ag reflective film has x value of 0.33 or less and y value of 0.35 or less, thereby preventing discoloration of the reflective film. At this time, if the color coordinate is out of the range of x and y values, the yellowish color is generated in the reflective film, and then the yellowish phenomenon appears as a whole.

As described above, according to the present invention, the cleaning process using the contact angle measuring device as described above is fairly stable, provides excellent cleaning ability to remove organic contaminant layers, and improves alignment film printability, thereby providing a cleaning method that can prevent alteration of the reflective film. By using this, it is possible to manufacture a liquid crystal display device of excellent quality with improved reflectance.

Hereinafter, the Example and comparative example of this invention are described. However, the following examples illustrate the present invention and do not limit the present invention.

EXAMPLE

Examples 1-1 to 1-3 and Comparative Examples 1-1 to 1-6

In the case of using ITO (Indium tin oxde) film as the pixel electrode during LCD manufacturing process, cleaning process evaluation (DI) and alignment film (PI) on ITO (Indium tin oxde) film by the contact angle meter while changing the cleaning conditions in the cleaning process The printability of (PI 7492) was measured (A, B, C, D, E, F correspond to any 6 point of 300 × 400 glass and are in the same position).

Cleaning evaluation

The result of measuring the contact angle by the washing process evaluation (DI) (organic contaminant removal evaluation) is shown in Table 1 below (unit: °).

division Cleaning method A B C D E F Average Comparative Example 1-1 No washing 39.64 42.54 41.14 46.09 46.16 45.61 43.53 Comparative Example 1-2 Ozone water 24.25 24.62 22.89 23.56 - - 23.83 Comparative Example 1-3 Organic cleaning - 18.87 22.05 22.63 22.18 - 21.43 Comparative Example 1-4 DI cleaning 29.42 29.47 26.7 27.47 27.67 27.78 28.08 Comparative Example 1-5 Hydrogen water 23.67 28.15 23.51 25.63 25.36 - 25.26 Comparative Example 1-6 DI (MS) 30.44 29.92 30.74 30.27 29.98 30.22 30.26 Example 1-1 UV cleaning after DI cleaning 16.31 15.76 16.24 16.15 16.66 16.66 16.3 Example 1-2 UV cleaning after organic cleaning 15.67 16.21 17.22 - - 17.32 16.6 Example 1-3 TMAH cleaning 2.38% 15.63 14.12 13.06 16 14.66 15.61 14.85

According to the results of Table 1, except for Examples 1-1 to 1-3, and Comparative Examples except Comparative Examples 1-1 and 1-6, the contact angle measurement was less than 30 °, Examples 1-1 to 1 -3 is lower than the contact angle measurements compared to the comparative examples it can be seen that the organic contaminant removal ability is excellent. That is, the present invention was further subjected to UV cleaning as in Examples 1-1 and 1-2 to lower the average contact angle to 16.3 and 16.6 degrees, respectively, superior to the organic layer removal ability than the conventional comparative examples. In particular, when washed with tetramethylammonium hydroxide (TMAH) of Example 1-3, it can be seen that the average contact angle is 14.85 °, the ability to remove the organic contaminant layer is large. That is, the ability to remove the organic contaminant layer is in the order of TMAH cleaning-organic cleaning, UV cleaning-DI cleaning, UV cleaning> organic cleaning-ozone water> hydrogen water> DI cleaning. 1 to 3 show contact angle measurement photographs for Examples 1-1 to 1-3 (UV cleaning after organic cleaning, UV cleaning after DI cleaning, and TMAH cleaning).

PI printability evaluation

The result of measuring the contact angle of the alignment film PI (PI printability evaluation) is shown in Table 2 below (unit: °). 4 and 5 show Examples 1-2 to 1-3 and Comparative Examples 1-3 (UV cleaning after organic cleaning, and contact angle measurement pictures for TMAH cleaning, respectively.

Cleaning method A B C D E F Average Comparative Example 1-1 No washing 13.1 14.3 14.77 14.42 14.98 13.82 14.23 Comparative Example 1-2 Ozone water 13.38 13.88 14.34 15.52 15.65 15.68 14.74 Comparative Example 1-3 Organic cleaning 4.24 2.79 5.56 4.87 4.26 - 4.34 Comparative Example 1-4 DI cleaning 14.44 15.86 15.42 15.9 16.57 14.98 15.53 Comparative Example 1-5 Hydrogen water 13.68 13.76 13.85 13.62 14.42 14.67 14 Comparative Example 1-6 DI (MS) 13.59 13.54 15.44 16.1 15.9 - 14.91 Example 1-1 UV cleaning after DI cleaning 16.24 17.33 16.41 15.98 17.49 16.95 16.73 Example 1-2 UV cleaning after organic cleaning 7.82 5.47 8.37 8.47 7.36 8.1 7.59 Example 1-3 TMAH cleaning 2.38% 4.47 4.55 5.95 6.77 5.38 4.99 5.35

In the results of Table 2, in the PI printability of the ITO film, Examples 1-2 and Examples 1-3 had an average contact angle of 7.59 and 5.35 °, which improved printability. However, in Example 1-1, the organic contaminant removal ability was excellent in the above, but the average contact angle was increased to 16.73 ° in PI printability. In addition, in the case of Comparative Examples 1-3, PI printability was improved.

However, in order to improve both organic contaminant removal ability and PI printability, UV cleaning or TMAH cleaning after organic cleaning as in Examples 1-2 and 1-3 is processally stable and excellent in removing organic contaminant layers. Able to know. Therefore, it can be seen that in the process using ITO as the pixel electrode, TMAH cleaning or UV cleaning after organic cleaning is an essential cleaning for removing the organic contaminant layer and PI printability.

Example 2-1 and Comparative Examples 2-1 to 2-9

When Ag was used as the reflective film during the LCD manufacturing process, the organic contaminant removal ability and PI printability were measured by each cleaning.

Cleaning evaluation

The organic fouling layer removal ability results are shown in Table 3 below (Measurement of contact angle on Ag film by DI: evaluation of organic layer removal, unit: °).

Cleaning method 1pt 2pt 3pt 4pt 5pt Average Comparative Example 2-1 Refer. (Ag) 51.1 52.59 52.01 47.37 49.87 50.588 Comparative Example 2-2 DI cleaning 59.54 55.84 56.87 56.98 59.51 57.748 Comparative Example 2-3 DI cleaning (MS) 42.35 44.78 44.3 45.75 44.56 44.348 Comparative Example 2-4 Ozone water cleaning 43.41 42.64 42.79 43.66 42.01 42.902 Comparative Example 2-5 Hydrogen water washing 37.01 39.41 38.63 39.56 39.47 38.816 Comparative Example 2-6 Reduced water washing 48.36 44.54 48.09 52.19 46.18 47.872 Comparative Example 2-7 Oxidized water cleaning 36.31 32.05 41.28 41.78 39.9 38.264 Comparative Example 2-8 TMAH (Ag) 47.11 47.39 47.93 49.42 49.44 48.258 Comparative Example 2-9 UV cleaning 26.74 28.2 29.76 26.88 28.75 28.066 Example 2-1 Organic cleaning 27.23 20.52 26.7 28.4 25.08 25.586

In Table 3, the organic contaminant layer removal on the Ag film by the contact angle measuring device is the best organic cleaning of Example 2-1, unlike ITO, TMAH cleaning did not have a significant effect.

PI printability evaluation

The degree of printability of the alignment film (PI) by washing can be represented by a contact angle measurement by the PI (5150), and the results of the contact angle measurement (PI printing evaluation) by the PI are shown in Table 4 below (unit: °).

A B C D E F Spread Comparative Example 2-1 No washing 7.93 7.9 8.4 7.88 7.57 7.82 - Comparative Example 2-2 DI cleaning 8.07 7.89 7.09 7.91 6.64 6.74 0.8 cm Comparative Example 2-3 DI (MS) 6.09 5.95 6.66 7.65 7.66 6.91 0.8 cm Comparative Example 2-5 Hydrogen water 8.13 7.87 7.29 8.5 8.3 9.44 0.8 cm Comparative Example 2-7 Oxidation water 6.21 5.49 5.95 6.07 5.95 6.24 0.9 cm Comparative Example 2-10 TMAH0.0238% 8.44 7.79 8.03 7.68 5.89 5.35 - Comparative Example 2-11 TMAH0.238% 7.22 7.83 6.92 6.75 5.69 5.67 - Example 2-1 Organic cleaning - - - 5.66 3.77 3.59 3.0 cm Example 2-2 DI cleaning after organic cleaning 3.65 - - 5.19 5.28 4.3 2.9 cm

As shown in Table 4, in Example 2-1 and 2-2, the printability of the alignment film (PI) was the best in the degree of PI printability by organic cleaning and the spreading degree was the best at the same time. In particular, DI cleaning after the organic cleaning of Example 2-2 showed more excellent results. Figure 6 shows the contact angle measurement by DI cleaning after organic cleaning.

Example 3-1 and 3-2

(DI cleaning after organic cleaning)

In order to show the yellowish phenomenon of the Ag reflecting film according to each cleaning, it was measured by using a spectroscopic reflectometer (MCPD) after the following process.

<Process sequence>

MCPD → Various cleaning on Ag (see Table 3) → MCPD

As a result, the yellow film of Ag film did not appear before and after each cleaning.

The results of the organic contaminant layer removal, PI printability, and yellowish phenomenon for the cleaning of Ag and ITO used in the reflective transmission type among the various cleaning conditions are shown in Table 5 below. 7 is shown.

Pixel film quality Washing method DI contact angle PI contact angle PI printability Yellow Wish Example 3-1 Ag (Weather) DI washing 25.6˚ ~ 4˚ Good No change Example 3-2 ITO TMAH cleaning (2.38%) 14.8˚ 5.35˚ Good -

In Table 5, it can be seen that discoloration of the reflective film can be prevented by lowering the contact angle measurement value by performing post-organic DI cleaning or TMAH cleaning according to the pixel film quality. That is, in the case of Ag film of Example 3-1, the contact angles were all lower than 30 °, and thus, the organic stain removal ability was excellent and the PI printability was good. In addition, in the case of the ITO film quality of Example 3-2, the contact angles were all lower than 30 °, and thus the organic contamination removal ability was excellent and the PI printability was also obtained.

As described above, the present invention uses the cleaning method of cleaning the ITO deposition film or Ag reflector in the LCD manufacturing process and then selecting the cleaning method having the best organic contaminant removal ability and the printability of the alignment film (PI) by measuring the contact angle on the film. Discoloration of Ag, which is a reflective film, can be prevented and a liquid crystal display device having improved printability of the alignment film PI can be provided.

Claims (7)

In the cleaning method of a semiconductor element, A method of cleaning a semiconductor device, the method comprising: cleaning with tetramethylammonium hydroxide (TMAH) after deposition of an indium tin oxde (ITO) film in a manufacturing process of a liquid crystal display device. The method of claim 1, wherein the tetramethylammonium hydroxide (TMAH) has a concentration of 0.7 to 5%. In the cleaning method of a semiconductor element, A method of cleaning a semiconductor device, the method comprising: cleaning with UV after organic cleaning after deposition of an indium tin oxde (ITO) film in a manufacturing process of a liquid crystal display device. In the cleaning method of a semiconductor element, In the manufacturing process of the liquid crystal display device, a method of cleaning a semiconductor device comprising the step of organic cleaning after the Ag reflective film deposition and washing with deionized water (DI). According to claim 3 or 4, wherein the organic cleaning is 20 to 60% by weight of monoethanolamine, 15 to 50% by weight of N, N-dimethylacetamide, 15 to 50% by weight of carbitol, and gallic acid A method of cleaning a semiconductor device, characterized in that it is carried out with an organic cleaning solution or photoresist stripping solution containing 0.1 to 10% by weight. The method of claim 1, wherein the UV cleaning is performed at 200 to 400 nm. A liquid crystal display device comprising the cleaning method according to any one of claims 1 to 6.