Composition for photoactivated etching of silicon dioxode films

FIELD: chemistry.

SUBSTANCE: invention can be used in producing integrated microcircuits and other electronic devices which use a planar manufacturing technique based on photolithographic processes. The composition for photoactivated etching of silicon dioxide films includes a polymer base - polymethyl methacrylate, a photosensitive component - ammonium fluoride in trifluoroacetic acid solution, a solvent - acetone, a protophilic agent - diphenylamine.

EFFECT: invention simplifies the process of producing a photoetched pattern on a silicon layer, increases the rate of photoetching and significantly reduces defects in the obtained articles.

1 tbl, 4 ex

 

The invention relates to the field of microelectronics, in particular the production of integrated circuits and other electronic devices using planar photolithography.

Known photopolymerizable composition for dry film photoresist, which are used to retrieve the image in the manufacture of printed circuit boards in the electronic industry (patent RF №2163724, 7G03C 1/72, H01L 31/08, publ. 2001.02.27). Known composition includes a copolymer of styrene and mono-n-butylmalonate, difunctional acrylate, 1-chloro-2-hydroxy-3-methacryloxypropyl, inhibitor, photoinitiator, dye and connection glycol. A disadvantage of known composition is its composition, which requires the introduction of photoinitiators for the implementation of photochemical reactions.

Known photolithography process without the use of stage manifestations, which implements the dry transfer of the pattern from the resist on Si02 using a reaction between silicon dioxide with pairs of HF at temperatures above 100°C. as catalysts for the process of etching composition using an organic base and peroxide compounds affecting the mechanism of the etching process (study of the reaction of the etching on the border of the silicon dioxide film resist process of the photolithography stage without symptoms. Studies on the interfacial etching reaction of devlopment-free vapor photolithography/Xiaoyin Hong, Lu Jianping, Duan Shengquan, Chen Qidao, Wang, Peiqing // J.Vac.Sci. and Technol. B. - 1999. - 17, 5. - C.2090-2095). For carrying out process a substrate covered with a film of photopolymer-based cinnamate containing 5-nitroacenaphthene as a photosensitive component and catalyst for the etching. There is a method of lithography allows to exclude the operation of manifestation and zadabrivaniya photoresist.

A disadvantage of known composition is the need to introduce in its catalyst composition, and the impossibility of using the composition for a photolithography process to avoid a stage of etching, which involves feeding into the system of toxic hydrogen fluoride HF at an elevated temperature.

Famous photo composition for etching films of silicon dioxide without the use of stages of manifestation, zadabrivaniya and etching, based on the reaction of the donor-acceptor interactions in non-aqueous solvents using as a light-sensitive photoactive component, ammonium fluoride, and as profiling reagent and simultaneously a solvent for the polymer base of polymethylmethacrylate is used pyridine (Photo composition for etching films of silicon dioxide. RF patent №2330049). The composition is selected as a prototype.

A disadvantage of known composition is a little soon the th etching (of 0.26 μm/min), as well as the use of toxic solvent is pyridine.

The task of the claimed invention to provide compositions for photo etching films of silicon dioxide SiO2in the processes of photolithography with high etching rate, which leads to simplification of the production process photolithographic pattern in the silicon layer and a substantial decrease in the defects of the products obtained.

The problem is solved in that, as in the prototype, the composition for photo etching films of silicon dioxide includes a polymer base poly (methyl methacrylate) (PMMA) and a photosensitive component, the ammonium fluoride solution triperoxonane acid, but unlike the prototype of the solvent used safe acetone, and as profiling reagent - diphenylamine in the following ratio, wt.%: polymethylmethacrylate 5,6-6,5; ammonium fluoride 4,0-4,6; diphenylamine 16,6-19,2; acetone 45,3-52,2; triperoxonane acid 21,3-24,6.

The main feature of the new photo composition is the release of F-ions due to donor-acceptor interaction of NH4+-acid and profiling of diphenylamine reagent, followed by ammonia (equation 1):

The anion F-h is obojdetsya in the system, further, the UV irradiation-formed active anion-radicals of fluorine, which poisoned the film of silicon dioxide (equations 2, 3):

For carrying out the invention take the components in the mass ratio, are presented in the claims.

Below is a staged preparation of solutions a, B and C required to obtain the composition for photo etching.

Example 1. First prepare a solution, which take a portion of about 0.50 g of polymethylmethacrylate PMMA and pour approximately 5.0 ml of acetone. The mixture was thoroughly stirred with a glass rod and incubated until complete dissolution of PMMA (about 24 hours). Then in the solution And injected approximately 1.50 g of diphenylamine, mixed with a glass rod for about 30 minutes until complete dissolution of diphenylamine and obtain solution B.

To prepare the solution In take out a portion of approximately 0.34 g of ammonium fluoride NH4F, pour in to 1.48 ml triperoxonane acid CF3COOH and mix thoroughly. Thus, there is a heating of the resulting mixture, after 3-5 minutes is the complete dissolution of NH4F.

The solution is poured to the solution and mixed. Thus there is little heating of the mixture and the viscosity increase of the solution. The resulting composition for a photo is aktivirovannogo etching was incubated for 1-2 hours until complete dissolution of all components. The claimed composition for photo etching films of silicon dioxide with one of the quantitative combinations of the components ready. After preparation, the composition retains its properties during the month.

Below are examples illustrating the application of the invention.

Example 2. On a silicon wafer with a layer of SiO2thickness of 0.35 μm, pre-cleaned in ethyl alcohol from dirt, put a pipette 1 drop of photo composition prepared according to example 1. The plate is irradiated under the lamp DRL-250 up to the full release of the film of silicon dioxide, which is time-45 with irradiated spot wash with acetone with a cotton swab, watching the complete removal of SiO2.

The velocity V photochemical etching in example 2 is 0.47 μm/min. at the same time determine the rate of chemical etching, going without UV irradiation. She is negligible and is 0.02 μm/min In a further contribution of this component is ignored.

Example 3. Prepare solutions a and B of example 1. To prepare the solution In weigh 0.32 g of ammonium fluoride NH4F and pour 1.5 ml triperoxonane acid CF3COOH, mix thoroughly. Thus, there is a heating of the resulting mixture, after 3-5 minutes is the complete dissolution of NH4F. the Solutions B and C are mixed and incubated within 1-2 hours until complete dissolution of all components. On a silicon wafer with a layer of SiO2thickness of 0.35 μm, cleansed from impurities in ethanol, applied by irrigation method 3 ml of the obtained composition for photo etching. Then the plate is irradiated under the lamp DRL-250 irradiated spot with a cotton swab gently washed with acetone until complete removal of SiO2that occurs within 37 seconds.

The velocity V photochemical etching in example 3 is 0.56 μm/min

Example 4. Prepare solutions a and B of example 1. To prepare the solution In weigh 0.34 g of ammonium fluoride NH4F, pour triperoxonane acid CF3COOH (1.5 ml), stirred thoroughly. Thus, there is a heating of the resulting mixture, after 3-5 minutes is the complete dissolution of NH4F. the Prepared solution is poured to the solution, the solutions are mixed, incubated for 1-2 hours until complete dissolution of all components. On a silicon wafer with a layer of SiO2thickness of 0.35 μm, cleansed from impurities in ethyl alcohol, applied with a pipette 1 drop of the obtained composition for photo etching. The plate is irradiated under the lamp DRL-250 up to the full release of the film of silicon dioxide, which occurs in 30 C. the Irradiated spot wash with acetone with a cotton swab, watching the complete removal of SiO2.

The velocity V fot the chemical etching in example 4 is 0.70 μm/min

Table
Comparative data on the rate of etching according to the invention and the prototype presented in the table.
The concentration of ammonium fluoride NH4F, g/ml0,0350,0490,052
The etching rate V, µm/minon
invention
0,47 (example 2)0,56 (example 3)0,70 (example 4)
on
prototype
0,260,26settling in sediment

The data show that the rate of etching composition according to the invention in 2 and more times higher compared with the composition of the prototype, especially at high concentrations, for which the composition of the prototype unattainable.

The main advantage of the claimed invention is to substantially increase the speed of photoetching, to 0.70 μm/min down from 0.26 μm/min in the prototype that allows to reduce the time photoexposure. The use of a composition according to the invention retains DOS is onsto prototype: completely excluded the stage of manifestation, zadabrivaniya and etching, which account for the largest number of defects and distortions of the circuit pattern. Etching S1O2 and removing etching products takes place at the stage of exposure. Eliminates the use of toxic solvent of pyridine and its utilization. Thus, photoetching using the claimed compositions more effectively in the field of microelectronics.

Sources of information

1. RF patent №2163724, publ. 27.02.2001.

2. J.Vac.Sci. and Technol. Century - 1999. - 17, 5. - S-2095.

3. RF patent №2330049, publ. 27.07.2008. The prototype.

Composition for photo etching films of silicon dioxide, including a polymer base poly (methyl methacrylate), a photosensitive component ammonium fluoride, triperoxonane acid and protophilic reagent, characterized in that as profiling reagent used diphenylamine, and the solvent is acetone, in the following ratio, wt.%:

Polymethylmethacrylate5,6-6,5
The ammonium fluoride4,0-4,6
Diphenylamine16,6-19,2
Acetone45,3-52,2
Triperoxonane the I acid from 21.3 to 24.6



 

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