KR101603565B1 - Developer Composition For Color Filter Image Sensor - Google Patents

Abstract

The present invention relates to a developer composition for a color filter image sensor. More specifically, the purpose of the present invention is to provide a developer composition for a color filter image sensor, which exhibits superior developability to form more uniform patterns while not remaining photoresist residues on a substrate after the development. To this end, the developer composition of the present invention comprises: a water-soluble polymer represented by chemical formula 1; at least one sort of nonionic surfactants represented by chemical formula 2 or 3; and an alkali compound.

Description

[0001] The present invention relates to a developer composition for a color filter image sensor,

The present invention relates to a developer composition for a color filter image sensor which is excellent in residue removal property.

An image sensor is a semiconductor device that converts an optical image into an electrical signal and displays or stores the electrical signal on a display device. Application areas of image sensors are increasing exponentially because of their wide use such as digital camera, mobile phone camera, camcorder, security device, car black box and medical device.

In general, image sensors are divided into two types: a charge coupled device (CCD) and a complementary metal oxide semiconductor (CMOS) image sensor (CIS). The image sensor has a plurality of pixels, and each pixel outputs a pixel signal corresponding to the incident light. At this time, each of the plurality of pixels accumulates light charges corresponding to the incident light through the photoelectric conversion elements represented by the photodiodes, and outputs the pixel signals based on the accumulated light charges.

A color image pickup device used for a solid state image pickup device (CCD) or a complementary metal oxide semiconductor image sensor (CIS) has a filter segment of additive mixed primary color of red, green and blue on the light receiving element A color filter having a filter segment is installed and the color is decomposed.

In recent years, the pattern size of a color filter mounted on such a color imaging device has been reduced to 1 / 100th to 1 / 200th of that of a color filter pattern for a conventional LCD. Thus, the color filter mounted on the color imaging device has become a more important item in which the performance is influenced by the increase of the resolution and the reduction of the residue.

Therefore, there is a need to develop a method for preventing the residue from remaining by providing a developer composition using a material capable of reducing the residue during development.

As a technique for improving the residue removal performance as described above, Korean Patent Registration No. 1174082 entitled " Pigment dispersion composition, photosensitive resin composition for color filter comprising the same, and color filter manufactured using the same, " (B) a monomer represented by the following formula (1); (C) a dispersant comprising a compound represented by the following formula (2); (D) a binder resin comprising a cationic binder resin represented by the following formula (3); And (E) a solvent, which can reduce the residue of a pattern and improve the resolution, a photosensitive resin composition for a color filter comprising the same, and a color filter manufactured using the composition. . Korean Patent Registration No. 0904068 " Photosensitive resin composition for color filter and color filter using the same " discloses a photosensitive resin composition for a color filter which comprises (a) an acrylic resin, (b) a photopolymerizable monomer, (c) a photopolymerization initiator, (A) the acrylic resin is a copolymer containing as a repeating unit an ethylenic unsaturated monomer having a carboxyl group and an alkoxy 4-oxobutanoate group, and (b) the photopolymerizable monomer Wherein the photosensitive resin composition comprises a glycerol methacrylate having a structure represented by the following formula (2). A photosensitive resin composition for a color filter and a color filter using the same, which can produce a high-resolution color filter with excellent residue characteristics and capable of producing fine pixels, are disclosed.

Korean Patent Publication No. 1174082 Korean Patent Registration No. 0904068

It is an object of the present invention to provide a developer composition for a color filter image sensor which is excellent in developing ability to form a pattern more uniformly without leaving a photoresist residue on a substrate after development.

In order to achieve the above object, the present invention provides a water-soluble polymer represented by the following formula (1): At least one nonionic surfactant represented by the following formula (2) or (3); And an alkaline compound. The present invention also provides a developer composition for a color filter image sensor.

[Chemical Formula 1]

In Formula 1, n is an integer of 1 to 50.

(2)

In Formula 2, R is H or OH, and x, y, and z are each an integer selected from 0 to 100.

(3)

In Formula 3, w, x, y, and z are integers selected from 0 to 20, respectively.

In one preferred embodiment of the present invention, the alkaline compound is selected from the group consisting of tetraethylammonium hydroxide, tetramethylammonium hydroxide, tetrabutylammonium hydroxide, potassium hydroxide, sodium hydroxide, sodium phosphate, sodium silicate, Sodium, and the like.

In one preferred embodiment of the invention, the composition comprises, based on the total weight of the composition, from 0.1 to 5% by weight of a water-soluble polymer, from 0.01 to 5% by weight of a nonionic surfactant, from 0.1 to 5% by weight of an alkaline compound, .

In a preferred embodiment of the present invention, a color filter manufactured using the developer composition for the color filter image sensor is provided.

According to a preferred embodiment of the present invention, there is provided an image sensor including the color filter.

The developer composition for a color filter image sensor according to the present invention is capable of forming a pattern more uniformly without leaving a photoresist residue on a substrate after development.

Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In general, the nomenclature used herein is well known and commonly used in the art.

Throughout this specification, when an element is referred to as "including " an element, it is understood that the element may include other elements as well, without departing from the other elements unless specifically stated otherwise.

In the present invention, 'photoresist' is a mixture of a polymer and a photosensitizer, and its chemical properties are changed by light. When the polymer is exposed to light of a certain wavelength, the solubility of the polymer in a specific solvent is changed. The dissolution rate of the exposed part and the non-exposed part is different, and when the dissolving time is over a certain time, it means that the part which is insoluble and insoluble remains to form the pattern.

In the present invention, 'color filter' refers to a key component for expressing color in a CMOS image sensor or the like applied to a digital camera, a mobile phone camera, or the like.

In the present invention, the term 'image sensor' refers to a semiconductor device that converts an optical image into an electrical signal and displays or stores the electrical signal on a display device.

In the present invention, the term 'wafer' refers to a thin circular plate that is a main material used for making a semiconductor integrated circuit, that is, a thin plate of thin single crystals such as silicon or gallium arsenide.

An embodiment of the present invention relates to a water-soluble polymer represented by the following formula (1); At least one nonionic surfactant represented by the following formula (2) or (3); And an alkaline compound. The present invention also provides a developer composition for a color filter image sensor.

[Chemical Formula 1]

In Formula 1, n is an integer of 1 to 50.

(2)

In Formula 2, R is H or OH, and x, y, and z are each an integer selected from 0 to 100.

(3)

In Formula 3, w, x, y, and z are integers selected from 0 to 20, respectively.

The composition may comprise 0.1 to 5 wt% of a water-soluble polymer, 0.01 to 5 wt% of a nonionic surfactant, 0.1 to 5 wt% of an alkaline compound, and the remainder in deionized water, based on the total weight of the composition.

The water-soluble polymer preferably comprises 0.1 to 5% by weight based on the total weight of the composition. If the water-soluble polymer is used in an amount of less than 0.1% by weight, development residues are produced. When the water-soluble polymer is used in an amount of more than 5% by weight, the development speed is significantly lowered.

The nonionic surfactant preferably comprises 0.01 to 5% by weight based on the total weight of the composition. If the nonionic surfactant is used in an amount of less than 0.01% by weight, development residue may be formed. If the nonionic surfactant is used in an amount exceeding 5% by weight, the development speed may rapidly increase and a desired pattern may not be formed. not.

The alkaline compound may be at least one selected from the group consisting of tetraethylammonium hydroxide, tetramethylammonium hydroxide, tetrabutylammonium hydroxide, potassium hydroxide, sodium hydroxide, sodium phosphate, sodium silicate, sodium carbonate, sodium hydrogen carbonate Or more.

Further, it is preferable that the alkaline compound contains 0.1 to 5% by weight based on the total weight of the composition. If the alkaline compound is used in an amount less than 0.1% by weight, the development is not properly performed. If the alkaline compound is used in an amount exceeding 5% by weight, the development speed is too high and the pattern is disadvantageous.

As described above, the developer composition for a color filter image sensor of the present invention provided from the present invention includes both the water-soluble polymer represented by the formula (1), the at least one nonionic surfactant represented by the formula (2) It is possible to provide a developer composition which is excellent in developing performance without leaving a photoresist residue on the substrate after development.

Another embodiment of the present invention may be applied to a color filter manufactured using the developer composition for the color filter image sensor, and may be applied to an image sensor including the color filter. An example of a process for obtaining a color filter manufactured using the developer composition for a color filter image sensor is as follows. First, a resist for an image sensor color filter is applied onto a wafer by a suitable method such as spin coating or slit coating. After the application of the resist, light is irradiated to form a pattern necessary for a color filter for an image sensor, and baking is carried out at an appropriate temperature. After the light irradiation, the development process is performed using the developer composition for an image sensor. When the light is irradiated as described above, the unexposed portions of the coating layer are dissolved and a pattern necessary for the image color filter is formed. By repeating this process according to the required number of red, green and blue colors, it is possible to obtain an image sensor color filter having a desired pattern.

[Example]

Hereinafter, the present invention will be described in more detail with reference to Examples. It is to be understood by those skilled in the art that these embodiments are only for illustrating the present invention and that the scope of the present invention is not construed as being limited by these embodiments.

Example 1

3 g of a nonionic surfactant with R = H, x = 12, y = 9 and z = 0 in formula (2), 3 g of a water-soluble polymer with n = 20 in formula 0.8 g of a nonionic surfactant with y = 4 and z = 4 and 2 g of tetramethylammonium hydroxide as an alkaline compound were charged with 91.2 g of deionized water (DI) and mechanically stirred for 12 hours, Mu] m, 0.02 [mu] m filter diameter to prepare a developer composition.

The wafer having the color filter photoresist pattern was treated by a spin method to confirm the residue removal property.

In the color filter development process, an organic film was coated on a silicon wafer using a spin coater, baked at 200 ° C for 5 minutes, coated with a color filter photoresist, and baked at 100 ° C for 3 minutes. Thereafter, the wafer was exposed to light at an exposure dose of 100 mJ / cm ² , washed with deionized water (DI) at 25 ° C for 1 minute, washed with deionized water (DI), dried by a spin method and then hard baked at 200 ° C for 5 minutes. As a result of measuring with a CD-SEM (Hitachi S-8820 series), a color filter photoresist pattern was formed in which all the residue was removed.

Example 2

3 g of a nonionic surfactant having R = H, x = 12, y = 9 and z = 0 in the formula (2), 3 g of a water- 0.8 g of nonionic surfactant with y = 4 and z = 4, and 91.2 g of deionized water were added to 2 g of tetramethylammonium hydroxide as an alkaline compound. After mechanical stirring for 12 hours, 0.1, 0.05, and 0.02 The solution was filtered in three stages using a filter having a diameter of 쨉 m to prepare a developer composition. The wafers were treated in the same manner as in Example 1 to confirm the residue removability.

Example 3

3 g of a nonionic surfactant having R = H, x = 12, y = 7 and z = 0 in formula (2), 3 g of a water-soluble polymer having n = 30 in formula 0.8 g of nonionic surfactant with y = 4 and z = 4, and 91.2 g of deionized water were added to 2 g of tetramethylammonium hydroxide as an alkaline compound. After mechanical stirring for 12 hours, 0.1, 0.05, and 0.02 The solution was filtered in three stages using a filter having a diameter of 쨉 m to prepare a developer composition. The wafers were treated in the same manner as in Example 1 to confirm the residue removability.

Example 4

3 g of a water-soluble polymer having n = 40 in the formula (1), 3 g of a nonionic surfactant having R = H, x = 12, y = 9 and z = 0 in the formula (2), w = 6, x = 0.8 g of nonionic surfactant with y = 4 and z = 4, and 91.2 g of deionized water were added to 2 g of tetramethylammonium hydroxide as an alkaline compound. After mechanical stirring for 12 hours, 0.1, 0.05, and 0.02 The solution was filtered in three stages using a filter having a diameter of 쨉 m to prepare a developer composition. The wafers were treated in the same manner as in Example 1 to confirm the residue removability.

Example 5

3 g of a nonionic surfactant having R = H, x = 12, y = 9 and z = 0 in formula (2), 3 g of a water-soluble polymer having n = 50 in formula 0.8 g of nonionic surfactant with y = 4 and z = 4, and 91.2 g of deionized water were added to 2 g of tetramethylammonium hydroxide as an alkaline compound. After mechanical stirring for 12 hours, 0.1, 0.05, and 0.02 The solution was filtered in three stages using a filter having a diameter of 쨉 m to prepare a developer composition. The wafers were treated in the same manner as in Example 1 to confirm the residue removability.

Example 6

3 g of a nonionic surfactant having R = H, x = 12, y = 7 and z = 0 in the formula (2), 3 g of a water- 0.8 g of nonionic surfactant with y = 4 and z = 4, and 91.2 g of deionized water were added to 2 g of tetramethylammonium hydroxide as an alkaline compound. After mechanical stirring for 12 hours, 0.1, 0.05, and 0.02 The solution was filtered in three stages using a filter having a diameter of 쨉 m to prepare a developer composition. The wafers were treated in the same manner as in Example 1 to confirm the residue removability.

Example 7

In a 200 ml flask, 3 g of a water-soluble polymer having n = 20 in formula (1), 3 g of a nonionic surfactant having R = H, x = 12, y = 9 and z = 1 in formula (2) 0.8 g of nonionic surfactant with y = 4 and z = 4, and 91.2 g of deionized water were added to 2 g of tetramethylammonium hydroxide as an alkaline compound. After mechanical stirring for 12 hours, 0.1, 0.05, and 0.02 The solution was filtered in three stages using a filter having a diameter of 쨉 m to prepare a developer composition. The wafers were treated in the same manner as in Example 1 to confirm the residue removability.

Comparative Example 1

The wafers were treated in the same manner as in Example 1 except that 2 g of tetramethylammonium hydroxide was used as an alkaline compound except for the water-soluble polymer of Chemical Formula 1 and the nonionic surfactants of Chemical Formula 2 and 3 in Example 1 And the residue removability was confirmed.

Comparative Example 2

3 g of a nonionic surfactant having R = H, x = 12, y = 9 and z = 1 in the formula (2) except for the water-soluble polymer of the formula (1) in Example 1, w = 6, x = 6, y = 4, z = 4, and 2 g of tetramethylammonium hydroxide as an alkaline compound were charged with 94.2 g of deionized water, mechanically stirred for 12 hours, and then filtered through 0.1 μm, 0.05 μm and 0.02 μm filtration And filtered through three stages using a filter having a diameter to prepare a developer composition. The wafers were treated in the same manner as in Example 1 to confirm the residue removability.

Comparative Example 3

3 g of a water-soluble polymer having n = 20 in Chemical Formula 1 and 3 g of nonionic surfactant w = 6, x = 6, y = 4 and z = 4 in Chemical Formula 3, except for the nonionic surfactant of Chemical Formula 2, and 97.2 g of deionized water was added to 2 g of tetramethylammonium hydroxide as an alkaline compound. The mixture was mechanically stirred for 12 hours, and then filtered in three stages using a filter having a filtration diameter of 0.1 탆, 0.05 탆 and 0.02 탆, respectively To prepare a developer composition. The wafer was treated in the same manner as in Example 1 to confirm the residue removability.

Characterization

The residue removability of the above Examples 1 to 7 and Comparative Examples 1 to 3 was measured. The residue removability was measured using CD-SEM (Hitachi S-8820 series). The criteria for the result are as follows.

<Residue Removability>

1. Very poor: less than 30% removed

2. Defective: 50% removed

3. Medium: 70% removed

4. Good: 80% removed

5. Very good: Over 90% removed

 The results thus obtained are shown in Table 1 below.

Residue Removability Example 1 5 Example 2 4 Example 3 4 Example 4 3 Example 5 3 Example 6 4 Example 7 4 Comparative Example 1 One Comparative Example 2 2 Comparative Example 3 2

As can be seen from the above and Table 1, Examples 1 to 7 were excellent in the removability of residues compared to Comparative Examples 1 to 3, and Comparative Examples 1 to 3 were found to be poor in residue removal or very poor.

As a result, it has been confirmed that when the developer composition for a color filter image sensor of the present invention is included in an optimum amount, a developer composition excellent in developing power can be provided without leaving a photoresist residue on the substrate after development.

It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.

Claims (5)

A water-soluble polymer represented by the following formula (1);
At least one nonionic surfactant represented by the following formula (2) or (3); And
A developer composition for a color filter image sensor, comprising an alkaline compound.
[Chemical Formula 1]

In Formula 1, n is an integer of 1 to 50.

(2)

In Formula 2, R is H or OH, x, y, and z are integers selected from 0 to 100, and when any one of x, y, and z is 0, the remaining is selected from 1 to 100 Lt; / RTI &gt;

(3)

In Formula 3, w, x, y, and z are integers selected from 0 to 20, respectively.
The method of claim 1, wherein the alkaline compound is selected from the group consisting of tetraethylammonium hydroxide, tetramethylammonium hydroxide, tetrabutylammonium hydroxide, potassium hydroxide, sodium hydroxide, sodium phosphate, sodium silicate, sodium carbonate, Wherein the color filter image sensor is at least one member selected from the group consisting of the following.
The composition according to claim 1, wherein the composition comprises 0.1 to 5% by weight of a water-soluble polymer, 0.01 to 5% by weight of a nonionic surfactant, 0.1 to 5% by weight of an alkaline compound, &Lt; / RTI &gt; for a color filter image sensor.
A color filter produced using the developer composition for a color filter image sensor of any one of claims 1 to 3.
An image sensor comprising a color filter according to claim 4.