KR20130016797A - High performance nitride etching composition and method of etching - Google Patents
High performance nitride etching composition and method of etching Download PDFInfo
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- KR20130016797A KR20130016797A KR1020110078920A KR20110078920A KR20130016797A KR 20130016797 A KR20130016797 A KR 20130016797A KR 1020110078920 A KR1020110078920 A KR 1020110078920A KR 20110078920 A KR20110078920 A KR 20110078920A KR 20130016797 A KR20130016797 A KR 20130016797A
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- silicate
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K13/00—Etching, surface-brightening or pickling compositions
- C09K13/04—Etching, surface-brightening or pickling compositions containing an inorganic acid
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
- H01L21/0271—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers
- H01L21/0273—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers characterised by the treatment of photoresist layers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
- H01L21/0271—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers
- H01L21/0273—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers characterised by the treatment of photoresist layers
- H01L21/0274—Photolithographic processes
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Abstract
Description
The present invention is an etching composition having an etching selectivity ratio of the nitride film and the oxide film and
Etching method, and more specifically using the etching composition in the semiconductor process, it is possible to minimize the etching rate for the oxide film while maintaining the etching rate of the nitride film
It relates to a fine etching method.
In the semiconductor fabrication process, silicon nitride (Si3N4) is physically and chemically
As a stable thin film, an insulating film, a dielectric film, a protective film, an etch stop film, etc. in a semiconductor device
It is used a lot. In addition, the silicon nitride film has a dielectric as compared to the silicon oxide film.
Excellent properties in terms of strength, mechanical strength, water vapor barrier, sodium barrier, etc.
The frequency of use is increasing gradually. But the semiconductor device
As it is miniaturized and highly integrated, it is necessary to compensate for the interference between devices.
There is a need to maintain the selectivity of the cone oxide film and silicon nitride film.
The development activities for various etchant with the etching selectivity between nitride and oxide
It's going on.
The conventional technique for etching the nitride film is to phosphoricate the wafer on which the silicon nitride film is formed.
Into the etching bath containing this, the phosphorus nitride was heated to 157 to 165 占 폚 to form a nitride film.
Etching by acid (Phosphoric acid) has been used. Such conventional etching
According to the process, the etching rate for the silicon nitride film is about 50 mW / min, and
The oxide film shows a level of about 1 to 2 dB / min. In addition, the selectivity ratio of the nitride film / oxide film at this time
Shows about 50: 1 level. If the selectivity of silicon nitride film and silicon oxide film is low
When secured, the oxide film is etched, which makes it difficult to separate devices.
In addition, due to the moisture contained in the phosphoric acid itself,
Additional selectivity will be reduced. In order to prevent this, the conventional technology
How to secure the selection ratio by adjusting the water content of phosphoric acid and fire as inorganic acid
Etching method comprising an etching solution containing acid, sulfuric acid, nitric acid, etc. and having an etching selectivity
Has been selected.
However, this conventional technique has resulted in a decrease in selectivity over time.
The method of bringing the selection ratio to the amount of water is not easy due to the rapid loss of moisture during high temperature processes.
There is also a problem of delaying the process time because additional supply must be made.
Was
Therefore, an object of the present invention is to ensure the etching rate of the stable nitride film and
To provide a highly selective etching solution that does not show etching ability to the oxide film
I put the purpose
As mentioned above, the present invention provides an etching selectivity for the nitride film and the oxide film.
It provides about the etching solution composition and its method. The provided etchant composition is an etchant
The etching rate of the nitride film is maintained at the existing level and higher than that of the tetraalkylammonium silicide.
Due to the action of the etching solution containing tetraalkylammonium silicate
Minimize the etching effect of the etching target (oxide) in the etching liquid in the area of the oxidized film
Especially useful.
In detail, the silicon nitride film and the silicon oxide film were etched using the etching composition.
Etch rate is 60 ~ 70Å / min, silicon oxide film at 157 ℃ ~ 165 ℃
0 ~ 0.2Å / min, and the ratio of etchrates is about 300 ~ ∞
A large number of etching selectivity is secured.
The calculation formula for calculating the etching rate is
{Initial film thickness (Å)-film thickness after treatment} / treatment time (min) = processing speed (Å / min)
The formula for calculating the ratio of etchrates is
Silicon Nitride Etch Rate (Å / min) / Silicon Oxide Etch Rate (Å / min) = Etch Selectivity
Silicones containing 0.05 to 1 percent by weight of tetraalkylammonium silicate in detail
The etching solution of the nitride film has excellent etching selectivity for the silicon nitride film and the silicon oxide film.
to provide. However, when the tetraalkylammonium silicate exceeds the composition ratio, the nitride film
Etching speed is secured, but silicon-based particles tend to be excessively precipitated.
Because of this, it is inefficient, and if it is lower than the composition ratio, the etching speed is secured.
Will not appear.
[Formula 1]
Tetraalkylammonium silicate used as an etchant in the etchant is
As a clathrate compound, a three-dimensional skeletal structure as shown in [Formula 1]
Silicate is dispersed in the Alkylammonium structure of
In [Formula 1] R1, R2, R3 and R4 are independently of each other hydrogen, methyl, ethyl,
n-propyl, iso-propyl selected from Alkylammonium of [Formula 1]
As a specific example of silicate, tetraethylammonium (Tetraethylammonium)
silicate, Tetramethylammonium silicate,
Selected from the group of tetrapropylammonium silicate
.
The main technique of the present invention is Alkyl ammonium ion
It acts as a buffer in phosphoric acid to facilitate dispersion of Silicate particles in phosphoric acid
do.
Alkyl ammonium ion is possible as a buffer because Tetraalkylammonium Silicate
Alkylammonium ion and silicate as a clathrate compound
Is not chemically bonded and dissolved in the form of salt
It is a door.
In addition, the improvement of the etching selectivity for the nitride film and the oxide film through silicon particles has been improved.
However, problems such as particle precipitation have been caused.
Therefore, in the present invention, perchloric acid, nitric acid, hydrofluoric acid, sulfuric acid, and salts derived from them.
1 species selected from the group consisting of Tetralklylammonium silicate
To make the solution easier and to break down the silicon particles to a certain size
It was added at 0.01 to 10% by weight.
In accordance with the technical background of the invention the actual silicon nitride film and silicon oxide film formed
Etching velocity of silicon nitride film as a result of immersing the wafer in the etching composition according to the present invention
Etchrate is represented by 60 to 70 Å / min, the etching rate of the silicon oxide film is
The selectivity ratio between the silicon nitride film and the silicon oxide film is 300 to ∞ at a rate of 0 to 0.2 Å / min.
Has brought an excellent effect of indicating
According to the present invention, when using an etching composition containing Alkylammonium ion
Excellent etching selectivity for cone nitride film and silicon oxide film is secured
Even when it was possible, it was possible to secure the same selection costs as the initial stage.
The representative figure is a figure showing the change of the etching rate according to the concentration of the additive of Example 1,
1 is a view showing a change in etching rate according to the number of batches of the first embodiment.
In the representative figure, the selectivity increases with the concentration of the additive,
1 is an etching rate graph according to the number of batches or does not change significantly depending on the number of batches
You can see that. 1 is also available for a long time as an etchant of the present invention
This figure identifies
The present invention will be described in detail based on the following Comparative Examples and Examples.
In the following evaluation method, after the etching solution was heated to 157 to 165 ° C., the nitride film and the oxide film were removed.
The formed wafer was immersed to measure the etching rate and the etching selectivity with time.
In Comparative Table 1, 85% phosphoric acid was heated, and the etch rates and
Selectivity was measured, and Comparative Examples 2 to 8 added a silicon compound to 85% phosphoric acid.
Etch rate and selectivity were measured.
Examples 1-3 add Tetraalkyl ammonium silicate and inorganic acids to 85% phosphoric acid
Etching rate and etching selectivity when measured
Table 1
Sillicon Compound of Tetraalkylammonium silicate and other structure according to the present invention
Even with, the improvement of etching selectivity in 85% phosphoric acid can be seen,
When compared to the tetraalkylammonium silicate evaluation, relatively little improvement was achieved.
Seemed. In addition, a composition containing Tetraalkylammonium silicate compound was added to 85% phosphoric acid.
When I was prepared, I could see the selectivity increase by several hundred times.
Claims (7)
The remaining ingredients are characterized in that it comprises phosphoric acid and deionized water
Nitride Etching Solution
The etch rate improver is a clathrate compound (ammonium compound)
Tetraethylammonium Silicates Containing Ions and Silicon Ions
silicate), tetramethylammonium silicate,
Selected from the group of tetrapropylammonium silicate
Nitride film etching solution
Nitride film etching solution, characterized in that selected from the group consisting of salt
Nitride film etching method comprising a process
Nitride etching is characterized in that the etching rate is maintained at 0.5 angstroms or less per minute
solution
a) forming a nitride film on the substrate and
b) etching the nitride film to form a gate electrode;
c) forming an insulating layer on the gate electrode;
d) forming a semiconductor layer on the gate insulating layer;
e) etching the nitride film in the step of forming source and drain electrodes on the semiconductor layer
Selective nitride film etching method comprising a step of
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| KR1020110078920A KR20130016797A (en) | 2011-08-09 | 2011-08-09 | High performance nitride etching composition and method of etching |
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| KR1020110078920A KR20130016797A (en) | 2011-08-09 | 2011-08-09 | High performance nitride etching composition and method of etching |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20180109429A (en) * | 2017-03-28 | 2018-10-08 | 동우 화인켐 주식회사 | Etchant composition for etching nitride layer and method of forming pattern using the same |
| US10689572B2 (en) | 2018-02-09 | 2020-06-23 | Ltcam Co., Ltd. | Etchant composition with high selectivity to silicon nitride |
| KR102345842B1 (en) * | 2020-09-21 | 2021-12-31 | 주식회사 이엔에프테크놀로지 | Silicon nitride layer etching composition and etching method using the same |
| EP4041845A4 (en) * | 2019-10-09 | 2023-11-22 | Entegris, Inc. | Wet etching composition and method |
-
2011
- 2011-08-09 KR KR1020110078920A patent/KR20130016797A/en not_active Application Discontinuation
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20180109429A (en) * | 2017-03-28 | 2018-10-08 | 동우 화인켐 주식회사 | Etchant composition for etching nitride layer and method of forming pattern using the same |
| US10689572B2 (en) | 2018-02-09 | 2020-06-23 | Ltcam Co., Ltd. | Etchant composition with high selectivity to silicon nitride |
| EP4041845A4 (en) * | 2019-10-09 | 2023-11-22 | Entegris, Inc. | Wet etching composition and method |
| KR102345842B1 (en) * | 2020-09-21 | 2021-12-31 | 주식회사 이엔에프테크놀로지 | Silicon nitride layer etching composition and etching method using the same |
| US20220089952A1 (en) * | 2020-09-21 | 2022-03-24 | Enf Technology Co., Ltd. | Silicon nitride film etching composition and etching method using the same |
| US11939505B2 (en) | 2020-09-21 | 2024-03-26 | Enf Technology Co., Ltd. | Silicon nitride film etching composition and etching method using the same |
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