CN115595154A - Selective etching solution for SiGe and Si - Google Patents
Selective etching solution for SiGe and Si Download PDFInfo
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- CN115595154A CN115595154A CN202211054794.0A CN202211054794A CN115595154A CN 115595154 A CN115595154 A CN 115595154A CN 202211054794 A CN202211054794 A CN 202211054794A CN 115595154 A CN115595154 A CN 115595154A
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- C—CHEMISTRY; METALLURGY
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- C09K13/00—Etching, surface-brightening or pickling compositions
- C09K13/04—Etching, surface-brightening or pickling compositions containing an inorganic acid
- C09K13/08—Etching, surface-brightening or pickling compositions containing an inorganic acid containing a fluorine compound
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- C—CHEMISTRY; METALLURGY
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- C09K13/00—Etching, surface-brightening or pickling compositions
- C09K13/04—Etching, surface-brightening or pickling compositions containing an inorganic acid
- C09K13/10—Etching, surface-brightening or pickling compositions containing an inorganic acid containing a boron compound
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Abstract
The invention belongs to the field of integrated circuit electronic chemicals, and particularly relates to a preparation method and a use method of a selective etching solution of SiGe and Si. The etching solution is mainly used for wet etching of SiGe, has good selectivity on SiGe, is weak in corrosion on Si, and mainly comprises 1-15% of a composite oxidant, 1-15% of a fluorine source, 30-60% of a buffer composition, 0.05-5% of a chelating agent and high-purity water. The etching solution not only has good selectivity to SiGe, but also has higher service life, and the etching rate and the selectivity ratio can be controlled by the component content and the temperature.
Description
Technical Field
The invention belongs to the field of electronic chemicals, and particularly relates to preparation and a using method of a selective etching solution of SiGe and Si.
Background
The introduction of a fin field effect transistor (FinFET) reduces the supply voltage and provides better electrical control of the channel, thereby reducing leakage current and overcoming short channel effects. A significant feature of a FinFET is that the gate wraps around three sides of the conductive channel "Fin". To further improve the performance of CMOS devices, shrinking the size while introducing high mobility materials such as Ge, the next era in CMOS should also introduce a concept of "GAA (gate all around) FET", which can be regarded as an extension of the current FinFET devices. GAA FETs, which feature a gate wrapped around the four sides of the channel, can further improve short channel control, are considered a key design feature for future CMOS technologies.
Selectively removing SiGe from the SiGe and Si multilayer stack of the fin results in a vertically stacked Si nanowire; vice versa, selectively removing Si from the same multilayer stack of fins results in vertically stacked SiGe nanowires. The method mainly aims at selectively removing SiGe in the SiGe and Si multilayer lamination, and has various modes for increasing the selectivity of the etching solution to SiGe, such as reasonably selecting an oxidant and a fluorine source, adjusting the pH value, adjusting the etching temperature, increasing the polarity of the etching solution and the like. Currently, the etching for selectively removing SiGe by SiGe/Si has various problems, such as high etching temperature, low selectivity and the like. The selectivity of the etching solution of the invention to SiGe is more than 30, the reaction temperature is low, and the etching rate and the selectivity ratio of SiGe can be controlled.
Disclosure of Invention
The invention aims to solve the problems of high etching temperature, low SiGe selectivity and the like of the existing etching solution for selectively etching SiGe, and aims to provide a preparation method and a use method of the SiGe selective etching solution with good selectivity and low etching temperature.
In order to achieve the purpose, the invention adopts the technical scheme that:
the selective etching liquid for SiGe and Si consists of composite oxidant 1-15 wt%, fluorine source 1-15 wt%, buffering composition 30-60 wt%, chelating agent 0.05-5 wt% and high purity water for the rest.
In the above scheme, the composite oxidant is an inorganic oxidant and an organic oxidant in a mass ratio of 1:1-10 to form the composite oxidant.
The inorganic oxidizing agent comprises at least one of hydrogen peroxide, peroxyacetic acid, perboric acid, ammonium persulfate, nitric acid and periodic acid;
the organic oxidant comprises at least one of benzoquinone, N-methylmorpholine-N-oxide, nitropyridine, nitrophenol, ureide, N-pyridine oxide and trimethylamine N-oxide.
In the above embodiment, the fluoride ion source includes at least one of hydrofluoric acid, ammonium fluoride, tetramethylammonium fluoride, tetraethylammonium fluoride, tetrapropylammonium fluoride, fluoroboric acid, ammonium bifluoride, hexafluorosilicic acid, hexafluorosilicate, triethylamine trihydrofluoric acid, pyridine hydrofluoride, and the like.
In the above scheme, the buffer composition is mainly an acetic acid-ammonium acetate buffer system, a citric acid-ammonium citrate buffer system, and preferably an acetic acid-ammonium acetate buffer system.
In the above embodiment, the chelating agent may be ethylenediaminetetraacetic acid, butanediamine tetraacetic acid, propylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid, tartaric acid, diethylenetriaminepentaacetic acid, thiosalicylic acid, ethylene glycol bis (2-aminoethyl ether) tetraacetic acid, cystine, gallic acid, or the like.
In the scheme, the used SiGe contains 30-60% of Ge (mass fraction), siGe materials with different Ge contents have different etching rates and selection ratios, the selection ratio of the invention to SiGe etching with Ge contents of more than 30% is greater than 30, and the higher the Ge content is, the higher the selectivity is, and when the Ge content in the SiGe is lower than 25%, the selective etching effect on the SiGe is not good due to the overlarge Si content, namely the selection ratio of the SiGe relative to Si is less than 15, and at this time, the selection ratio can be improved by changing conditions.
In the scheme, a certain amount of ultrapure water is added into a container, a certain amount of oxidant, a fluorine source, a chelating agent and organic acid are sequentially added into the ultrapure water, the mixture is uniformly stirred, the organic acid salt is added to adjust the pH value to 2.5-4.5, and the mixture is uniformly mixed to obtain the selective etching solution of SiGe and Si. The etching temperature range is 25-40 ℃.
In the scheme, the lining material of the container is HDPE, PFA or PTFE, and the precipitation amount of metal ions is less than or equal to 30w/10 -9 。
The invention has the advantages of
(1) The oxidant of the selective etching solution of SiGe and Si adopts organic and inorganic coordination, thereby not only ensuring the etching rate, but also increasing the selection ratio. In the process of wet etching SiGe and Si, oxidizing SiGe and Si by an oxidizing agent, and removing the oxides by a fluorine source, wherein the selectivity to SiGe is realized by balancing the oxidation rate and the oxide removal rate of SiGe and Si by changing the components of an etching solution or etching conditions, so that the oxidation rate and the oxide removal rate of SiGe are greatly increased, and the oxidation rate and the oxide removal rate of Si are reduced or slightly increased. The weak oxidizing agent oxidizes SiGe more strongly than Si, which also further increases the selectivity to SiGe.
(3) The organic buffer component of the etching solution has a large proportion, so that the surface tension is low, defoaming and wetting effects can be well achieved without adding a surfactant, the mass transfer resistance of the etching solution can be effectively reduced, the diffusibility of an etching product in the solution is improved, and the etching uniformity is maintained. The buffering pH value is 2.5-4.5, the etching temperature is 25-40 ℃, and the etching solution is relatively stable.
(4) The chelating agent can chelate heavy metal ions, thereby greatly reducing the natural loss of the oxidant and prolonging the service life of the etching solution.
Detailed Description
In order to better understand the present invention, the following examples are further provided to illustrate the present invention, but the present invention is not limited to the following examples.
Example 1
(1) The configuration method comprises the following steps: calculating the mass of each raw material for preparing the required etching solution according to the mass percentage, firstly weighing pure water with corresponding mass, placing the pure water into a container, then adding other components without specific sequence, wherein the components do not comprise ammonium acetate, uniformly mixing, then adjusting the pH value to 4.0 by using the ammonium acetate, and finally uniformly mixing to obtain the selective etching solution of SiGe and Si.
(2) Etching conditions: stirring and soaking at 30 ℃ for 200 r/min.
(3) Etching the test piece: siGe (30% Ge).
(4) Examples of etching solutions with different combinations of oxidizing agents.
Comparative example 1
(1) The configuration method comprises the following steps: calculating the mass of each raw material for preparing the required etching solution according to the mass percentage, wherein the oxidant is hydrogen peroxide, pure water with corresponding mass is weighed and placed in a container, other components without specific sequence are added, the pH value is adjusted to 4.0 by using ammonium acetate after the components are uniformly mixed, and finally the selective etching solution of SiGe and Si is obtained after the components are uniformly mixed.
(2) Etching conditions are as follows: stirring and soaking at 30 ℃ for 200 r/min.
(3) Etching the test piece: siGe (30% Ge).
(4) Hydrogen peroxide is used as an oxidant for etching liquid.
The methods of examples 2, 3 and 4 are the same as example 1, and only have different formulations, and the specific formula is as follows:
example 5
(1) The configuration method comprises the following steps: calculating the mass of each raw material for preparing the required etching solution according to the mass percentage, firstly weighing pure water with corresponding mass, placing the pure water into a container, then adding other components without specific sequence, wherein the components do not comprise ammonium acetate, uniformly mixing, then adjusting the pH value to 4.0 by using the ammonium acetate, and finally uniformly mixing to obtain the selective etching solution of SiGe and Si.
(2) Etching conditions: stirring and soaking at 30 ℃ for 200 r/min.
(3) Etching the test piece: siGe (30% Ge).
Examples 6-9 were carried out using different etchant solutions for different fluorine sources, as in example 5, but with different formulations:
example 10
(1) The configuration method comprises the following steps: calculating the mass of each raw material for preparing the required etching solution according to the mass percentage, firstly weighing pure water with corresponding mass, placing the pure water into a container, then adding other components without specific sequence, wherein the components do not comprise ammonium acetate and ammonium citrate, uniformly mixing, then adjusting the pH value to 4.0 by using ammonium acetate/ammonium citrate, and finally uniformly mixing to obtain the selective etching solution of SiGe and Si. .
(2) Etching conditions: stirring and soaking at 30 ℃ for 200 r/min.
(3) Etching the test piece: siGe (30% Ge).
(4) The different buffer system schemes are as in example 11:
comparative example 2
(1) The configuration method comprises the following steps: calculating the mass of each raw material for preparing the etching solution according to the mass percentage, firstly weighing pure water with corresponding mass, placing the pure water into a container, then adding other components without specific sequence, and obtaining the comparative etching solution without buffer components.
(2) Etching conditions: stirring and soaking at 30 ℃ for 200 r/min.
(3) Etching the test piece: siGe (30% Ge).
Examples 12 to 15
(1) The configuration method comprises the following steps: calculating the mass of each raw material for preparing the required etching solution according to the mass percentage, firstly weighing pure water with corresponding mass, placing the pure water into a container, then adding other components without specific sequence, wherein the components do not comprise ammonium acetate, uniformly mixing, then adjusting the pH value to 4.0 by using the ammonium acetate, and finally uniformly mixing to obtain the selective etching solution of SiGe and Si.
(2) Etching conditions: the temperature is specified (DEG C), and the mixture is stirred and soaked at the speed of 200 r/min.
(3) Etching the test piece: siGe (30% Ge).
(4) Different temperature etch protocol, as in examples 13, 14, 15:
examples 16 to 20
(1) The configuration method comprises the following steps: calculating the mass of each raw material for preparing the required etching solution according to the mass percentage, firstly weighing pure water with corresponding mass, placing the pure water into a container, then adding other components without specific sequence, wherein the components do not comprise ammonium acetate, uniformly mixing, then adjusting the pH value to a specified value by using the ammonium acetate, and finally uniformly mixing to obtain the selective etching solution of SiGe and Si.
(2) Etching conditions are as follows: stirring and soaking at 30 ℃ for 200 r/min.
(3) Etching the test piece: siGe (30% Ge).
(3) Examples of different pH etches:
examples 21 to 25
(1) The configuration method comprises the following steps: calculating the mass of each raw material for preparing the required etching solution according to the mass percentage, firstly weighing pure water with corresponding mass, placing the pure water into a container, then adding other components without specific sequence, wherein the components do not comprise ammonium acetate, uniformly mixing, then adjusting the pH value to a specified value by using the ammonium acetate, and finally uniformly mixing to obtain the selective etching solution of SiGe and Si.
(2) Etching conditions: stirring and soaking at 30 ℃ for 200 r/min.
(3) The etching schemes with different Ge contents are as follows:
example 21 test piece etching: siGe (20% Ge);
example 22 etch coupon: siGe (30% Ge);
example 23 test piece etching: siGe (40% Ge);
example 24 etch coupon: siGe (50% Ge);
example 25 test piece etching: siGe (60% Ge);
Claims (8)
1. a selective etchant for SiGe and Si, characterized by: the selective etching method for SiGe comprises the following main components of 1-15% of composite oxidant, 1-15% of fluorine source, 30-60% of buffer composition, 0.05-5% of chelating agent and the balance of high-purity water.
2. The selective etching solution for SiGe and Si according to claim 1, wherein: the composite oxidant is an inorganic oxidant and an organic oxidant in a mass ratio of 1:1-10 to form the composite oxidant.
3. The selective etching solution for SiGe and Si according to claim 1, wherein: the inorganic oxidant comprises at least one of hydrogen peroxide, peracetic acid, perboric acid, ammonium persulfate, nitric acid and periodic acid.
4. The selective etching solution for SiGe and Si according to claim 1, wherein: the organic oxidant comprises at least one of benzoquinone, N-methylmorpholine-N-oxide, nitropyridine, nitrophenol, alloxan, pyridine N-oxide and trimethylamine N-oxide.
5. The selective etching solution for SiGe and Si according to claim 1, wherein: the fluorine source comprises at least one of hydrofluoric acid, ammonium fluoride, tetramethyl ammonium fluoride, tetraethyl ammonium fluoride, tetrapropyl ammonium fluoride, ammonium bifluoride, fluoroboric acid, hexafluorosilicic acid, hexafluorosilicate, triethylamine trihydrofluoric acid and pyridine hydrofluoride compounds.
6. The selective etching solution for SiGe and Si as claimed in claim 1, wherein: the buffer composition is an acetic acid-ammonium acetate buffer system or a citric acid-ammonium citrate buffer system.
7. The selective etching solution for SiGe and Si as claimed in claim 1, wherein: the chelating agent is at least one of ethylenediamine tetraacetic acid, butanediamine tetraacetic acid, propanediamine tetraacetic acid, diethylenetriamine pentaacetic acid, triethylenetetramine hexaacetic acid, diethylenetriamine pentaacetic acid, tartaric acid, thiosalicylic acid, ethylene glycol bis (2-aminoethyl ether) tetraacetic acid, cystine and gallic acid.
8. The selective etching solution for SiGe and Si as claimed in claim 1, wherein: the SiGe material used contains 30-60% Ge.
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| CN202211054794.0A CN115595154A (en) | 2022-08-31 | 2022-08-31 | Selective etching solution for SiGe and Si |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104513983A (en) * | 2013-10-07 | 2015-04-15 | 易安爱富科技有限公司 | Etching liquid composition for copper-and-molybdenum-containing film |
| CN105733587A (en) * | 2014-12-29 | 2016-07-06 | 气体产品与化学公司 | Etchant solution and method of use thereof |
| CN108570678A (en) * | 2018-04-13 | 2018-09-25 | 深圳达诚清洗剂有限公司 | A kind of metal etch liquid applied to copper-molybdenum film layer |
| CN110240907A (en) * | 2018-03-09 | 2019-09-17 | 弗萨姆材料美国有限责任公司 | Etching solution for selectively removing silicon-germanium alloy from silicon-germanium/germanium stack during semiconductor device fabrication |
| CN111019659A (en) * | 2019-12-06 | 2020-04-17 | 湖北兴福电子材料有限公司 | Selective silicon etching liquid |
| CN111808612A (en) * | 2020-07-08 | 2020-10-23 | 江苏和达电子科技有限公司 | Etching solution and etching supplementary solution for copper/molybdenum (niobium)/IGZO film layer, and preparation method and application thereof |
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- 2022-08-31 CN CN202211054794.0A patent/CN115595154A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104513983A (en) * | 2013-10-07 | 2015-04-15 | 易安爱富科技有限公司 | Etching liquid composition for copper-and-molybdenum-containing film |
| CN105733587A (en) * | 2014-12-29 | 2016-07-06 | 气体产品与化学公司 | Etchant solution and method of use thereof |
| CN110240907A (en) * | 2018-03-09 | 2019-09-17 | 弗萨姆材料美国有限责任公司 | Etching solution for selectively removing silicon-germanium alloy from silicon-germanium/germanium stack during semiconductor device fabrication |
| CN108570678A (en) * | 2018-04-13 | 2018-09-25 | 深圳达诚清洗剂有限公司 | A kind of metal etch liquid applied to copper-molybdenum film layer |
| CN111019659A (en) * | 2019-12-06 | 2020-04-17 | 湖北兴福电子材料有限公司 | Selective silicon etching liquid |
| CN111808612A (en) * | 2020-07-08 | 2020-10-23 | 江苏和达电子科技有限公司 | Etching solution and etching supplementary solution for copper/molybdenum (niobium)/IGZO film layer, and preparation method and application thereof |
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