A low etching rate developer composition and preparation method thereof

Abstract

The invention discloses a low-etching rate developer composition and a preparation method thereof, comprising alkylnaphthalene sulfonate, nonionic surfactant, alkali metal salt, high-purity water, 0.2-10% of alkylnaphthalene sulfonate, 0.01-10% of nonionic surfactant, 0.1-10% of alkali metal salt and 70-96.9% of high-purity water. The photoresist developer of the invention has a low etching rate of substrate material, and the development process does not cause substrate corrosion. At the same time, the developer also has the characteristics of high dispersion stability, less foam, large operation window, clear development pattern, no post-photoresist residue and no substrate corrosion.

Description

Technical Field

[0001] The invention relates to the field of functional microelectronic materials, and in particular to a low-etching rate developer composition and a preparation method thereof. Background Art

[0002] Photolithography is an important step in the manufacturing process of display panels and semiconductor devices. In TFT-LCD, TP and semiconductor wafer manufacturing processes, almost all pattern transfers are completed by photolithography. The process flow of photolithography includes substrate pretreatment, photoresist coating, pre-baking, exposure, development, post-baking, etching or ion implantation, and photoresist removal. The substrate material is not only a glass substrate and a silicon wafer, but also other metal layers, dielectric layers, etc.

[0003] Currently, the developers used in the photolithography process are mainly TMHA and KOH developers. These two types of developers have strong corrosion properties on metal substrates, such as Al metal layers. TMAH and KOH developers are not suitable for developing such substrates. Therefore, a developer with a low etching rate on the substrate is needed. Summary of the invention

[0004] The technical problem to be solved by the present invention is a low etching rate developer composition and a preparation method thereof, which is suitable for a developer composition in a photolithography process in the field of TFT-LCD, TP and semiconductor. Compared with TMAH and KOH developers, the developer has a lower metal substrate etching rate, and also has the characteristics of high surface wettability, less foam, large operating window, clear pattern after development, no photoresist residue, etc.

[0005] The invention is realized by the following technical scheme: a low etching rate developer composition, comprising alkylnaphthalene sulfonate, nonionic surfactant, alkali metal salt, high-purity water, 0.2-10% of alkylnaphthalene sulfonate, 0.01-10% of nonionic surfactant, 0.1-10% of alkali metal salt and 70-96.9% of high-purity water.

[0006] As a preferred technical solution, the specific gravity of the alkylnaphthalene sulfonate is 0.5-5%, the specific gravity of the nonionic surfactant is 0.05-5%, the specific gravity of the alkali metal salt is 0.2-8%, and the specific gravity of the high-purity water is 82-99.25%.

[0007] As a preferred technical solution, the structural formula of the surfactant alkylnaphthalene sulfonate is, wherein M is one or more of Na, K, Mg, Al, and Ca, R is a straight or branched alkane with 1-20 C atoms, and the number of n is 1-5.

[0008] As a preferred technical solution, the nonionic surfactant is one or more of the series of long-chain fatty alcohol polyoxyethylene ether, alkylphenol polyoxyethylene ether, and polyol polyoxyethylene ether.

[0009] As a preferred technical solution, the alkali metal salt is one or more of sodium carbonate, potassium carbonate, sodium oxalate, potassium oxalate, sodium bicarbonate, potassium bicarbonate, sodium silicate, and potassium silicate.

[0010] As a preferred technical solution, high-purity water is deionized water with a resistance value greater than 10 mΩ / cm.

[0011] A method for preparing a low etching rate developer composition comprises the following steps:

[0012] 1. Add alkylnaphthalene sulfonate, nonionic surfactant, alkali metal salt, high-purity water, 0.2-10% of alkylnaphthalene sulfonate, 0.01-10% of nonionic surfactant, 0.1-10% of alkali metal salt and 70-96.9% of high-purity water into a stirring container in sequence for stirring and dissolving;

[0013] 2. During the dissolution process, the heat release of the strong alkali must be controlled, and the temperature of the entire dissolution process must be controlled below 50 degrees;

[0014] 3. After the solution is completely dissolved, filter it with a 0.1um filter element.

[0015] The beneficial effects of the present invention are as follows: the low etching rate developer of the present invention can be used directly or after dilution. The developer of the present invention has no special restrictions during use and can be used in an immersion or spraying manner.

[0016] The positive improvement effect of the present invention is that the photoresist developer of the present invention has a lower etching rate of the substrate material, and the development process will not cause substrate corrosion. At the same time, the developer also has the characteristics of high dispersion stability, less foam, large operation window, clear development pattern, no post-photoresist residue and no substrate corrosion. DETAILED DESCRIPTION

[0017] All features disclosed in this specification, or steps in all methods or processes disclosed, except mutually exclusive features and / or steps, can be combined in any manner.

[0018] The invention discloses a low etching rate developer composition, which comprises alkylnaphthalene sulfonate, nonionic surfactant, alkali metal salt, high-purity water, 0.2-10% of alkylnaphthalene sulfonate, 0.01-10% of nonionic surfactant, 0.1-10% of alkali metal salt and 70-96.9% of high-purity water.

[0019] In this embodiment, the specific gravity of the alkylnaphthalene sulfonate is 0.5-5%, the specific gravity of the nonionic surfactant is 0.05-5%, the specific gravity of the alkali metal salt is 0.2-8%, and the specific gravity of the high-purity water is 82-99.25%.

[0020] Among them, the nonionic surfactant is one or more of the series of long-chain fatty alcohol polyoxyethylene ether, alkylphenol polyoxyethylene ether and polyol polyoxyethylene ether.

[0021] The structural formula of the surfactant alkylnaphthalene sulfonate is Wherein M is one or more of Na, K, Mg, Al, and Ca, R is a straight or branched alkane with 1 to 20 C atoms, and the number of n is 1 to 5.

[0022] In this embodiment, the structural formula of long-chain fatty alcohol polyoxyethylene ether is as follows:

[0023]

[0024] Preferred are polyoxyethylene lauryl ether, polyoxyethylene alkyl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl dodecyl ether, etc.; the structural formula of alkylphenol polyoxyethylene ether is as follows:

[0025]

[0026] Preferred are nonylphenol polyoxyethylene ether, octylphenol polyoxyethylene ether, phenethylphenol polyoxyethylene ether, diphenylethylphenol polyoxyethylene ether, triphenethylphenol polyoxyethylene ether, dodecylphenol polyoxyethylene ether, isooctylphenol polyoxyethylene ether, cardanol polyoxyethylene ether, di-sec-butylphenol polyoxyethylene ether, polyoctylphenol polyoxyethylene ether, and p-cumylphenol polyoxyethylene ether.

[0027] The structural formula of the polyol polyoxyethylene ether is: RO(CH2CH2O)nH, wherein n is the degree of polymerization, and preferred glycerol fatty acid esters, propylene glycol fatty acid esters, monostearate sorbitan, monooleate sorbitan, sesquioleate sorbitan, coconut oil fatty acid sorbitan, monohexadecanoic acid sorbitan, tristearate sorbitan, trioleate sorbitan, monolaurate polyoxyethylene sorbitan, monohexadecanoic acid polyoxyethylene sorbitan, monostearate polyoxyethylene sorbitan, tristearate polyoxyethylene sorbitan, monooleate polyoxyethylene sorbitan, trioleate polyoxyethylene sorbitan, triisostearate polyoxyethylene sorbitan, tetraoleate polyoxyethylene sorbitan, etc. The nonionic surfactant is used together with alkyl naphthalene sulfonate, has a synergistic effect, and can enhance the stability of surface wetting and penetration effects.

[0028] In this embodiment, the alkali metal salt is one or more of sodium carbonate, potassium carbonate, sodium oxalate, potassium oxalate, sodium bicarbonate, potassium bicarbonate, sodium silicate, and potassium silicate, and the high-purity water is deionized water with a resistance value greater than 10 mΩ / cm.

[0029] In this embodiment, the preparation method of the low etching rate developer composition specifically includes the following steps:

[0030] (1) adding alkylnaphthalene sulfonate, nonionic surfactant, alkali metal salt, high-purity water, 0.2-10% of alkylnaphthalene sulfonate, 0.01-10% of nonionic surfactant, 0.1-10% of alkali metal salt and 70-96.9% of high-purity water to a stirring container in sequence for stirring and dissolving;

[0031] (2) During the dissolution process, the heat release of the strong base must be controlled, and the temperature of the entire dissolution process must be controlled below 50 degrees;

[0032] (3) After the solution is completely dissolved, filter it with a 0.1um filter element.

[0033] Table 1 Components and contents of the developer solutions of the embodiments and comparative examples:

[0034]

[0035]

[0036]

[0037]

[0038] Table 1.

[0039] In order to further investigate the wetting effect and developing effect of the developer, the present invention adopts the following technical means: 1. Wetting effect, the surface tension of the original solution and diluted solution samples of the above-mentioned embodiments and comparative examples is measured by using an HTYZL-H fully automatic tension tester; 2. Developer effect: On the glass substrate, a certain thickness of negative color photoresist is spin-coated and pre-baked in an oven at 120°C for 80s. Then use a pattern mask to expose, and after the exposure is completed, use the above-mentioned developer diluted 20 times for development. After the development treatment, wash with high-purity water, then dry with nitrogen, and hard bake in an oven at 220°C. Observe with an optical microscope and an electron microscope. Confirm the development effect. The properties of the high-concentration developer stock solution and the development effect after dilution are shown in Table 2;

[0040]

[0041]

[0042] Table 2.

[0043] It can be seen from Table 2 that the low etching rate developer of the present invention, as shown in Examples 1 to 10, has a lower surface tension and an excellent developing effect. Compared with Example 10, Comparative Example 1 has a higher surface tension because it contains only potassium oxalate and does not contain alkyl sulfonate and non-surfactant. At the same time, there are residues after development and the pattern is flawed and unclear.

[0044] Since Comparative Example 2 does not contain a nonionic surfactant, although it has a lower surface tension before dilution, the surface tension increases significantly after dilution, and a clear pattern with no residue and high precision cannot be obtained.

[0045] Comparative Example 3 does not contain alkyl sulfonate and has a high surface tension, so it is also impossible to obtain a residue-free, high-precision, clear pattern.

[0046] In summary, the invention has the following progressive significance: providing a low etching rate developer suitable for TFT-LCD, TP and semiconductor wafer manufacturing processes, the developer containing alkyl sulfonate, nonionic surfactant, alkali metal salt and high-purity water. The developer has a low metal substrate etching rate, and also has the characteristics of high surface wettability, less foam, large operating window, clear pattern after development, and no photoresist residue.

[0047] It should be understood that the wt % mentioned in the present invention refers to the mass percentage.

[0048] The beneficial effects of the present invention are as follows: the low etching rate developer of the present invention can be used directly or after dilution. The developer of the present invention has no special restrictions during use and can be used in an immersion or spraying manner.

[0049] The positive improvement effect of the present invention is that the photoresist developer of the present invention has a lower etching rate of the substrate material, and the development process will not cause substrate corrosion. At the same time, the developer also has the characteristics of high dispersion stability, less foam, large operation window, clear development pattern, no post-photoresist residue and no substrate corrosion.

[0050] The above is only a specific embodiment of the present invention, but the protection scope of the present invention is not limited thereto. Any changes or substitutions that are not conceived through creative work should be included in the protection scope of the present invention. Therefore, the protection scope of the present invention should be based on the protection scope defined in the claims.

Claims

1. A low etching rate developer composition, characterized in that: It is composed of alkylnaphthalene sulfonate, nonionic surfactant, alkali metal salt and high-purity water; the proportion of the alkylnaphthalene sulfonate is 0.2-10%, the proportion of the nonionic surfactant is 0.01-10%, the proportion of the alkali metal salt is 0.1-10%, and the proportion of the high-purity water is 70-96.9%; The structural formula of the alkylnaphthalene sulfonate is Wherein M is one or more of Na, K, Mg, Al, and Ca, R is a straight or branched alkane having 1 to 20 carbon atoms, and the number of n is 1 to 5; The nonionic surfactant is one or more of the series of long-chain fatty alcohol polyoxyethylene ether and polyol polyoxyethylene ether.

2. The low etching rate developer composition according to claim 1, characterized in that: The specific weight of the alkylnaphthalene sulfonate is 0.5-5%, the specific weight of the nonionic surfactant is 0.05-5%, the specific weight of the alkali metal salt is 0.2-8%, and the specific weight of the high-purity water is 82-99.25%.

3. The low etching rate developer composition according to claim 1, characterized in that: The alkali metal salt is one or more of sodium carbonate, potassium carbonate, sodium oxalate, potassium oxalate, sodium bicarbonate, potassium bicarbonate, sodium silicate and potassium silicate.

4. The low etching rate developer composition according to claim 1, characterized in that: High-purity water uses deionized water with a resistance value greater than 10mΩ / cm.

5. A method for preparing the low etching rate developer composition according to claim 1, characterized in that:

1. Add alkylnaphthalene sulfonate, nonionic surfactant, alkali metal salt, high-purity water, 0.2-10% of alkylnaphthalene sulfonate, 0.01-10% of nonionic surfactant, 0.1-10% of alkali metal salt and 70-96.9% of high-purity water into a stirring container in sequence for stirring and dissolving; 2. During the dissolution process, the heat release of the strong alkali must be controlled, and the temperature of the entire dissolution process must be controlled below 50 degrees; 3. After the solution is completely dissolved, filter it with a 0.1um filter element.

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