A developer composition

Abstract

The present invention discloses a developer composition, which comprises an organic amine, a surfactant and an organic solvent, wherein the organic amine is selected from one or more organic amines having a structure of formula I, formula II or formula III. The developer of the present invention can improve the roughness and defects of the straight line edge while ensuring the resolution, thereby expanding the window of the photolithography process by adding a specific organic amine.

Description

Technical Field

[0001] The invention relates to the technical field of semiconductor and packaging photolithography, and is used for development after exposure, in particular to a developer composition. Background Art

[0002] In the optical exposure process, in order to transfer the pattern on the mask to the wafer, the radiation must act on the photosensitive material, and the photosensitive material must change the material properties through light exposure so that the purpose of transferring the pattern can be achieved after the photolithography process is completed. This photosensitive material is called photoresist.

[0003] Photoresists are divided into positive and negative resists. Positive resists: The exposed areas are dissolved after development, and the non-exposed areas remain. Negative resists: The exposed areas are left after development, and the non-exposed areas are dissolved in the developer.

[0004] Currently, most photoresists used for 193nm lithography are positive photoresists. However, as semiconductor process nodes continue to shrink, it has become more challenging to use traditional positive photoresists with alkaline aqueous developer to print small features such as small-sized grooves and through holes, because the optical image contrast of the dark field mask used to produce grooves and through holes is poor. For this reason, the industry has proposed the concept of negative tone develop (NTD), which uses positive photoresist exposure and negative developer (rather than standard TMAH aqueous solution) to achieve the same effect as negative photoresist development. The use of negative development process also enables the bright mask to achieve narrower grooves on the positive photoresist.

[0005] Currently, the commonly used negative photoresist developers are NBA solution and THMA solution. Although these two developers can achieve good resolution, they are not very effective in improving LER. When the roughness LER is improved, the resolution will decrease, mainly because the dissolution rate is too fast. Therefore, how to improve the roughness while ensuring the resolution is what the technicians in this field are committed to solving. Summary of the invention

[0006] The purpose of the present invention is to overcome the shortcomings of the prior art and provide a developer composition that can improve the roughness and defects of straight line edges without affecting the resolution and expand the window of the photolithography process.

[0007] To achieve the above object, the technical solution adopted by the present invention is: a developer composition, the developer composition comprises an organic amine, a surfactant and an organic solvent, the organic amine is selected from one or more organic amines having a structure of formula I, formula II or formula III,

[0008]

[0009] Wherein, in formula II, R1 is selected from any one of -NH2 and -CH2-NH2, R2 is selected from any one of -H, -OH and -CH3, and n is an integer greater than or equal to 1.

[0010] Preferably, the surfactant is a nonionic surfactant.

[0011] As a specific implementation, the developer composition is composed of the following components in percentage by mass: organic amine: 0.01-1%, surfactant: 0.01-1%, and the balance is organic solvent.

[0012] As a specific implementation manner, R1 in the formula II is -NH2, and R2 is -H.

[0013] As a specific implementation, R1 in the formula II is -CH2-NH2, and R2 is -OH or -CH3.

[0014] As a specific implementation manner, n in Formula II is an integer from 1 to 20.

[0015] As a specific embodiment, the organic solvent is butyl acetate with a concentration of more than 95%.

[0016] Due to the application of the above technical solution, the present invention has the following advantages compared with the prior art: the developer of the present invention, by adding specific organic amines, can improve the roughness LER and defects of the straight edge while ensuring the resolution, thereby expanding the window of the photolithography process. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] Figures 1 to 6 The photoresist is developed with the developer in Examples 1 to 6 to form a pattern, and the roughness image of the 45 nm iso trench is observed using CD-SEM;

[0018] Figures 7 to 10 The photoresist was developed with the developer of Comparative Examples 1 to 4 to form a pattern, and the roughness image of the 45 nm iso trench was observed using CD-SEM. DETAILED DESCRIPTION

[0019] The technical solution of the present invention is further described below in conjunction with the accompanying drawings and specific embodiments.

[0020] Example 1

[0021] In this example, a developer composition is provided, which is obtained by stirring 0.5% of an organic amine, 0.5% of a surfactant, and 99% of an organic solvent at room temperature to obtain a developer S1.

[0022] Among them, the organic amine has the structural formula:

[0023]

[0024] The surfactant is a non-ionic surfactant, and the organic solvent uses butyl acetate with a concentration of more than 95%.

[0025] Example 2

[0026] In this example, a developer composition is provided, which is obtained by stirring 0.3% of an organic amine, 0.5% of a surfactant, and 99.2% of an organic solvent at room temperature to obtain a developer S2.

[0027] Among them, the organic amine has the structural formula:

[0028]

[0029] The surfactant is a non-ionic surfactant, and the organic solvent uses butyl acetate with a concentration of more than 95%.

[0030] Example 3

[0031] In this example, a developer composition is provided, which is obtained by stirring 0.1% of an organic amine, 0.5% of a surfactant, and 99.4% of an organic solvent at room temperature to obtain a developer S3.

[0032] Among them, the organic amine has the structural formula:

[0033]

[0034] The surfactant is a non-ionic surfactant, and the organic solvent uses butyl acetate with a concentration of more than 95%.

[0035] Example 4

[0036] In this example, a developer composition is provided, which is obtained by stirring 0.8% of an organic amine, 0.5% of a surfactant, and 98.7% of an organic solvent at room temperature to obtain a developer S4.

[0037] Among them, the organic amine has the structural formula:

[0038]

[0039] The surfactant is a non-ionic surfactant, and the organic solvent uses butyl acetate with a concentration of more than 95%.

[0040] Example 5

[0041] In this example, a developer composition is provided, which is obtained by stirring 0.8% of an organic amine, 0.2% of a surfactant, and 99% of an organic solvent at room temperature to obtain a developer S5.

[0042] Among them, the organic amine has the structural formula:

[0043]

[0044] The surfactant is a non-ionic surfactant, and the organic solvent uses butyl acetate with a concentration of more than 95%.

[0045] Example 6

[0046] In this example, a developer composition is provided, which is obtained by stirring 0.3% of an organic amine, 0.7% of a surfactant, and 99% of an organic solvent at room temperature to obtain a developer S6.

[0047] Among them, the organic amine has the structural formula:

[0048]

[0049] The surfactant is a non-ionic surfactant, and the organic solvent uses butyl acetate with a concentration of more than 95%.

[0050] Comparative Example 1

[0051] In this example, a developer composition is provided, which is obtained by stirring 1.2% of an organic amine, 0.5% of a surfactant, and 98.3% of an organic solvent at room temperature to obtain a developer C1.

[0052] Among them, the organic amine has the structural formula:

[0053]

[0054] The surfactant is a non-ionic surfactant, and the organic solvent uses butyl acetate with a concentration of more than 95%.

[0055] Comparative Example 2

[0056] In this example, a developer composition is provided, which is obtained by mixing 0.3% of an organic amine, 1.2% of a surfactant, and 98.5% of an organic solvent at room temperature and stirring to obtain a developer C2.

[0057] Among them, the organic amine has the structural formula:

[0058]

[0059] The surfactant is a non-ionic surfactant, and the organic solvent uses butyl acetate with a concentration of more than 95%.

[0060] Comparative Example 3

[0061] This example provides a developer composition, which is obtained by stirring 1% surfactant and 99% organic solvent at room temperature to obtain developer C3, the surfactant is a non-ionic surfactant, and the organic solvent uses butyl acetate with a concentration of more than 95%.

[0062] Comparative Example 4

[0063] In this example, a developer composition is provided, wherein 1% organic amine and 99.5% organic solvent are stirred at room temperature to obtain a developer C4.

[0064] Among them, the organic amine has the structural formula:

[0065]

[0066] The surfactant is a non-ionic surfactant, and the organic solvent uses butyl acetate with a concentration of more than 95%.

[0067] The developers obtained in Examples 1 to 6 and Comparative Examples 1 to 4 were tested, and the specific testing method is as follows:

[0068] On the silicon wafer coated with BARC (bottom anti-radiation coating), ArF-i photoresist with a film thickness of 850A was coated, and the soft baking (PAB) condition was 100 degrees for 60 seconds. The sample was also exposed to light, and the exposure machine was NIKON 610C, and the lighting condition was S0.80 / 0.64, XY. After the exposure, the sample was baked (PEB) at 85 degrees for 60 seconds. After the baking, it was developed, and the development time was 18 seconds. The developer was the embodiment 1-6 and comparative example 1-4 involved in this patent. After the pattern was formed, the roughness (LER) of the 45nm Iso trench was observed using CD-SEM

[0069] Photoresist pattern observation method: CD-SEM observation is used. The observation results are shown in Table 1. The specific pattern is shown in the attached Figures 1 to 6 , Figures 7 to 10 .

[0070] ○: The edge is clean and has no burrs or the edge of the pattern is smooth;

[0071] ×: The edge is not clean and has burrs or the edge of the pattern is not smooth.

[0072] Table 1

[0073]

[0074]

[0075] From Table 1, we can see that by using the developer of the present invention, the image obtained has good LER while ensuring the resolution.

[0076] The above embodiments are only for illustrating the technical concept and features of the present invention, and their purpose is to enable people familiar with the technology to understand the content of the present invention and implement it accordingly, and they cannot be used to limit the protection scope of the present invention. Any equivalent changes or modifications made according to the spirit of the present invention should be included in the protection scope of the present invention.

Claims

1. A developer composition suitable for a negative developing process of a positive photoresist, characterized in that: The developer composition comprises an organic amine, a surfactant and an organic solvent; the developer composition is composed of the following components in percentage by mass: 0.01-1% of the organic amine, 0.01-1% of the surfactant, and the balance of the organic solvent; the organic solvent is butyl acetate with a concentration of more than 95%; the organic amine is selected from one or more organic amines having a structure of formula I, formula II or formula III, ， Wherein, in formula II, R1 is selected from any one of -NH2 and -CH2-NH2, R2 is selected from any one of -H, -OH and -CH3, and n is an integer from 1 to 20.

2. The developer composition according to claim 1, characterized in that: The surfactant used is a nonionic surfactant.

3. The developer composition according to claim 1, characterized in that: In the formula II, R1 is -NH2 and R2 is -H.

4. The developer composition according to claim 1, characterized in that: In the formula II, R1 is -CH2-NH2, and R2 is -OH or -CH3.

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